CN113620349B - One-dimensional iron-based wave-absorbing material derived from metal organic framework and preparation method thereof - Google Patents
One-dimensional iron-based wave-absorbing material derived from metal organic framework and preparation method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 59
- 239000011358 absorbing material Substances 0.000 title claims abstract description 54
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 45
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000011324 bead Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 4
- 239000013384 organic framework Substances 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000009467 reduction Effects 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 19
- 230000035699 permeability Effects 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
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- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- B22F9/00—Making metallic powder or suspensions thereof
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Abstract
The invention discloses a one-dimensional iron-based wave-absorbing material derived from a metal organic framework and a preparation method thereof, belonging to the technical field of microwave absorbing materials. A one-dimensional metal organic framework (Fe-bdc) is used as a precursor, and the processes of air oxidation and hydrogen reduction are adopted, so that the regulation and control of the content and the morphology of magnetic components in the derived one-dimensional iron-based wave-absorbing material are realized, the optimization of electromagnetic parameters is promoted, and the effective absorption of broadband electromagnetic waves is realized under low thickness. From the aspect of composition, the oxidation process effectively removes non-magnetic components, and the reduction process effectively adjusts the content of each magnetic component. From the structure, the one-dimensional continuous bead-shaped structure has stronger shape anisotropy, can promote the formation of magnetic conduction and electric conduction paths, and is beneficial to the enhancement of the electromagnetic attenuation capability. The effective absorption frequency band of the one-dimensional iron-based wave-absorbing material can reach 3.52 GHz when the thickness is only 1.2 mm, and the one-dimensional iron-based wave-absorbing material shows excellent low-thickness broadband wave-absorbing characteristics. The process does not need complex equipment, has low cost and strong product consistency.
Description
Technical Field
The invention belongs to the technical field of microwave absorbing materials, and particularly relates to a metal organic framework derived one-dimensional iron-based wave absorbing material and a preparation method thereof.
Background
The 5G communication technology developed at a high speed greatly facilitates human life, but brings about the problem of increasingly serious electromagnetic pollution at the same time, and the development of efficient microwave absorbing materials is urgently needed. With the acceleration of the construction of small-sized 5G base stations and the upgrading and upgrading of a large number of microelectronic devices, the wide effective absorption frequency band and the low thickness have gradually become core targets for the research and development of wave-absorbing materials. According to the electromagnetic theory, the reduction of the thickness of the wave-absorbing material can be realized by improving the complex dielectric constant or complex magnetic permeability. Wherein the introduction of one-dimensional structures can be effectively reducedThe percolation threshold of the wave-absorbing material in the wave-transparent matrix promotes the formation of a conductive network, thereby improving the complex dielectric constant. For example, Ding et al prepared TiO by solvothermal methods2Nanowire and preparation of one-dimensional TiO by gas-phase polymerization process2@Fe3O4The material has an absorption band up to 6 GHz and a reflection loss peak up to-61.8 dB (at 2.2 mm thickness) (@ PPy)Small,2019, 15). Interestingly, the one-dimensional structure may also cause a change in the magnetic anisotropy, thereby affecting the complex permeability spectrum of the wave absorbing material. For example, when Shen et al successfully synthesizes an iron nanowire with a diameter of 100nm by a magnetic field-assisted hydrothermal method, the iron nanowire has higher saturation magnetization and coercive force and correspondingly increased complex permeability compared with the traditional nano-iron (1)Journal of Alloys and Compounds,2016,4). In addition, a number of studies have shown that the broadening of the effective absorption band is highly dependent on the increase in complex permeability and matching of complex permittivity. Li et al hydrothermal synthesis of Fe2O3@ PVP material, heat treated to form Fe3O4-Fe @ C core-shell material, wherein the magnetic Fe, Fe3O4Provides stronger magnetic loss, and the carbon shell greatly improves the dielectric loss capability of the material, so that the material can meet the absorption requirement under a Ku wave band under the thickness of 1.99 mm (Journal of Alloys and Compounds,2020, 821). Although researchers have overcome the problems of narrow effective absorption band and large matching thickness of some wave-absorbing material products through a plurality of means, how to realize broadening of the effective absorption band under the condition of low matching thickness still remains a difficult problem to be solved urgently, and meanwhile, simplification of the preparation process and improvement of product uniformity are also difficult points faced in the research and development of the wave-absorbing material.
Disclosure of Invention
In order to give consideration to the widening of an effective absorption frequency band and the reduction of matching thickness, the invention provides a one-dimensional iron-based wave-absorbing material derived from a metal organic framework and a preparation method of the one-dimensional iron-based wave-absorbing material derived from the metal organic framework.
A one-dimensional iron-based wave-absorbing material derived from a metal organic framework is gray black powder, and comprises iron, ferroferric oxide and ferrous oxide, wherein the mass fraction of iron element is 47.3-63.79%; the particles of the gray black powder are in a one-dimensional bead shape, the bead shape is a cylindrical bead, the length of the bead is 300-2000 nm, and the diameter of the bead is 20-1000 nm.
The preparation operation steps of the one-dimensional iron-based wave-absorbing material derived from the metal organic framework are as follows:
(1) dissolving 1.08 g of ferric chloride hexahydrate in 54 mL of N, N-dimethylformamide solution, stirring for 10 min, adding 0.88 g of terephthalic acid, and stirring for 30 min to obtain iron salt solution; dissolving 0.096 g of sodium hydroxide in 6 mL of deionized water, adding into the ferric salt solution, and carrying out solvothermal reaction at 100 ℃ for 24 h; the product was centrifuged and washed twice with N, N-dimethylformamide; drying for 1 hour in a vacuum drying oven at the temperature of 80 ℃; grinding to obtain metal organic framework powder; the metal organic framework powder is light yellow, iron is used as a central metal element, terephthalic acid is used as an organic ligand and is marked as Fe-bdc, particles of the metal organic framework powder are in a one-dimensional rod shape, the rod length is 1000 nm, and the diameter is 100 nm;
(2) taking 1 g of the metal organic framework powder, carrying out heat treatment in a muffle furnace under the air condition, raising the temperature to 450-650 ℃ at the speed of 2 ℃/min, preserving the heat for 4 hours, naturally cooling, and grinding to obtain metal organic framework derived iron oxide powder, wherein the metal organic framework derived iron oxide powder is red, the powder particles are rod-shaped, the rod length is 300-1000 nm, and the diameter is 20-100 nm;
(3) taking 0.5g of the metal organic framework derived iron oxide powder, reducing in a tubular furnace in a hydrogen atmosphere, heating to 350-550 ℃ at the speed of 2 ℃/min, preserving the temperature for 1 h, naturally cooling, and grinding to obtain the metal organic framework derived one-dimensional iron-based wave-absorbing material; the one-dimensional iron-based wave-absorbing material is gray black powder, and mainly comprises iron, ferroferric oxide and ferrous oxide, wherein the mass fraction of iron element is 47.3-63.79%; the powder particles are in the shape of one-dimensional beads, the beads are cylindrical beads, the length of the beads is 300-2000 nm, and the diameter of the beads is 20-1000 nm.
The beneficial technical effects of the invention are embodied in the following aspects:
1. the one-dimensional iron-based composite wave-absorbing material is obtained by using a metal organic framework as a precursor and adopting a method of oxidation and reduction. The effective regulation and control of the magnetic metal components, content and morphology in the derived iron-based wave-absorbing material can be realized by changing the redox conditions, the increase and optimization of complex permeability and complex dielectric constant are promoted, and further the broadening of an effective absorption band under low thickness is realized. From the aspect of composition, organic components of the precursor rod-shaped Fe-bdc are thoroughly removed after oxidation, and high content of magnetic components after reduction is ensured. The controllable hydrogen reduction realizes the adjustment of the reduction degree of the ferric oxide, and further realizes the change of the content of iron and the oxide thereof in the product, thereby adjusting the electromagnetic parameters. Structurally, after redox, the derivative product is in the shape of a bead and has strong shape anisotropy, so that the material shows high complex permeability, the small particle size of the product effectively limits the eddy current effect, and the wave absorbing performance in a high frequency range is improved. Due to the advantages, the effective absorption frequency range of the derived one-dimensional iron-based wave-absorbing material under the conditions that the filling degree is 60 wt% and the thickness is 1.2 mm can reach 14.48-18 GHz; the reflection loss peak value of the broadband wave absorbing material at 16.16 GHz under the thickness of 1.2 mm can reach-43.77 dB, and the broadband wave absorbing material shows excellent broadband wave absorbing performance with low matching thickness.
2. The invention takes the metal organic framework Fe-bdc synthesized by solvothermal synthesis as a precursor, and has high yield and strong consistency. The oxidation and reduction process belongs to a mature industrial production process, and the controllability is strong. The whole production process is simple, complex and expensive equipment is not needed, the production cost is low, the product consistency is high, and large-scale production can be realized.
Drawings
FIG. 1 is an SEM photograph of the prepared metal organic framework Fe-bdc.
FIG. 2 is an SEM photograph of the prepared metal organic framework Fe-bdc derived iron oxide.
FIG. 3 is an XRD spectrum of the one-dimensional iron-based wave-absorbing material S1 prepared in example 1.
FIG. 4 is an SEM photograph of the one-dimensional iron-based wave-absorbing material S1 prepared in example 1.
Fig. 5 is an electromagnetic parameter spectrum of the one-dimensional iron-based wave-absorbing material S1 prepared in example 1.
FIG. 6 is a reflection loss curve diagram of the one-dimensional iron-based wave-absorbing material S1 prepared in example 1.
FIG. 7 is an XRD spectrum of a one-dimensional iron-based wave-absorbing material S2 prepared in example 2.
FIG. 8 is an SEM photograph of the one-dimensional iron-based wave-absorbing material S2 prepared in example 2.
Fig. 9 is an electromagnetic parameter spectrum of the one-dimensional iron-based wave-absorbing material S2 prepared in example 2.
FIG. 10 is a reflection loss curve diagram of the one-dimensional iron-based wave-absorbing material S2 prepared in example 2.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
The specific preparation operation steps of the metal organic framework derived one-dimensional iron-based wave-absorbing material are as follows:
(1) dissolving 1.08 g of ferric chloride hexahydrate in 54 mL of N, N-dimethylformamide solution, stirring for 10 min, adding 0.88 g of terephthalic acid, and stirring for 30 min to obtain iron salt solution; dissolving 0.096 g of sodium hydroxide in 6 mL of deionized water, pouring the sodium hydroxide solution into the ferric salt solution, and carrying out solvothermal reaction at 100 ℃ for 24 h; after the reaction is finished, centrifugally separating a product, washing the product twice by using N, N-dimethylformamide, and drying the product for 1 hour in a vacuum drying oven at the temperature of 80 ℃; grinding to obtain metal organic framework powder; the metal organic framework powder is light yellow, iron is used as a central metal element, terephthalic acid is used as an organic ligand and is marked as Fe-bdc, particles of the metal organic framework powder are in a one-dimensional rod shape, the length of the rod is 1000 nm, and the diameter of the rod is about 100 nm.
(2) And (2) taking 1 g of the metal organic framework powder, carrying out heat treatment in a muffle furnace under the air condition, raising the temperature to 550 ℃ at the speed of 2 ℃/min, preserving the temperature for 4 h, naturally cooling, and grinding to obtain the metal organic framework derived iron oxide powder, wherein the metal organic framework derived iron oxide powder is red, the powder particles are rod-shaped, the rod length is 500 nm, and the diameter is 50 nm.
(3) Taking 0.5g of the metal organic framework derived iron oxide powder, reducing in a tubular furnace in a hydrogen atmosphere, heating to 350 ℃ at the speed of 2 ℃/min, preserving the temperature for 1 h, naturally cooling, and grinding to obtain the metal organic framework derived one-dimensional iron-based wave-absorbing material; the one-dimensional iron-based wave-absorbing material is gray black powder, and comprises iron, ferroferric oxide and ferrous oxide, wherein the mass fraction of iron element is 63.79%; the powder particles are in the form of one-dimensional beads which are cylindrical beads having a length of 1000 nm and a diameter of 100 nm.
Referring to fig. 1, the metal organic framework particles prepared in this example 1 have a one-dimensional rod-like structure, a length of about 1000 nm and a diameter of about 100 nm.
Referring to fig. 2, the volume of the iron oxide powder particles derived from the metal organic framework prepared in this example 1 is somewhat shrunk after being oxidized at 450 ℃, and meanwhile, partial holes appear on the rod-shaped surface, but the whole structure still maintains a one-dimensional rod-shaped structure. The material is now about 500 nm long and about 50 nm in diameter. According to the samples and experimental procedures, the phenomenon is caused because organic components in the material are oxidized and removed in the air, and metal elements are oxidized into ferric oxide (Fe) in the air2O3）。
Referring to fig. 3, an XRD spectrogram of the one-dimensional iron-based wave-absorbing material S1 prepared in this example 1 can see a plurality of distinct diffraction peaks, referring to ferroferric oxide (Fe)3O4) The diffraction peak in the graph corresponds well to the characteristic peak in the card and has no impurity peak. According to the ICP test result, the content of the iron element in the sample is 63.79 wt%, and analysis shows that the S1 product is reduced by hydrogen to form ferroferric oxide (Fe) with high crystallinity3O4）。
Referring to fig. 4, an SEM photograph of the one-dimensional iron-based wave absorbing material S1 prepared in this example 1. As can be seen, the material passes through 350oAfter C hydrogen reduction, the porous rod-like structure is changed into a one-dimensional structure of beads, the beads are cylindrical beads, the length is about 1000 nm, and the diameter is about 100 nm. The presence of one-dimensional beads is associated with the reduction of the material, i.e. the oxidation of the materialIron (Fe)2O3) Reducing the resulting ferroferric oxide (Fe)3O4) The particles grow gradually and are connected to each other.
Referring to fig. 5, a complex permittivity and complex permeability spectrogram of the one-dimensional iron-based wave-absorbing material S1 prepared in this example 1 with a filling degree of 60 wt%, as seen in fig. 5, the real part of the complex permittivity of S1 is in a significantly decreasing trend in the range of 14.20, 2-12 GHz when the complex permittivity changes from 23.72 at 2 GHz to 18 GHz. The imaginary part of the complex dielectric constant shows the trend of rising first and then falling, and an obvious peak appears at 10 GHz, which indicates that the dielectric relaxation phenomenon occurs at the moment and is beneficial to enhancing the polarization loss capability. This phenomenon may occur due to iron oxide (Fe)3O4) The existence of the middle two valence state iron (Fe) greatly improves the dielectric loss capability of the material. The real part of complex permeability and the imaginary part of complex permeability of S1 gradually decrease as a whole with increasing frequency, and the real part of complex permeability is about 1.65 and the imaginary part is about 0.50 at 2 GHz. The real part rises by a certain amount around 10 GHz. The macroscopic appearance of the material in the form of one-dimensional beads can be an important reason for forming a magnetic conduction path and improving the complex magnetic conductivity. In summary, S1 has both strong dielectric loss and magnetic loss capabilities.
Referring to fig. 6, in a reflection loss curve diagram of the one-dimensional iron-based wave-absorbing material S1 prepared in this embodiment 1, the peak value of the reflection loss of the material can reach-43.76 dB at 16.16 GHz with a thickness of 1.2 mm, and effective absorption at 14.48-18 GHz is achieved. It can be seen that S1 has excellent wave-absorbing properties at low thickness. The main component of the material is ferroferric oxide (Fe)3O4) And simultaneously has better dielectric loss and magnetic loss capability. The one-dimensional bead-shaped structure is beneficial to forming a magnetic conduction path, improves the magnetic conductivity of the material and further realizes excellent impedance matching and magnetic loss capability.
Example 2
The specific preparation operation steps of the metal organic framework derived one-dimensional iron-based wave-absorbing material are as follows:
(1) dissolving 1.08 g of ferric chloride hexahydrate in 54 mL of N, N-dimethylformamide solution, stirring for 10 min, adding 0.88 g of terephthalic acid, and stirring for 30 min to obtain iron salt solution; dissolving 0.096 g of sodium hydroxide into 6 mL of deionized water, adding the sodium hydroxide solution into the iron salt solution, and carrying out solvothermal reaction for 24 h at 100 ℃; after the reaction is finished, centrifugally separating a product, and washing twice by using N, N-dimethylformamide; drying for 1 hour in a vacuum drying oven at the temperature of 80 ℃; grinding to obtain metal organic framework powder; the metal organic framework powder is light yellow, iron is used as a central metal element, terephthalic acid is used as an organic ligand and is marked as Fe-bdc, particles of the metal organic framework powder are in a one-dimensional rod shape, the length of the rod is 1000 nm, and the diameter of the rod is about 100 nm.
(2) Taking 1 g of the metal organic framework powder, carrying out heat treatment in a muffle furnace under the air condition, raising the temperature to 450 ℃ at the speed of 2 ℃/min, preserving the heat for 4 h, naturally cooling, and grinding to obtain metal organic framework derived iron oxide powder, wherein the metal organic framework derived iron oxide powder is red, the powder particles are rod-shaped, the length is 500 nm, and the diameter is 50 nm;
(3) taking 0.5g of the metal organic framework derived iron oxide powder, reducing in a tubular furnace in a hydrogen atmosphere, raising the temperature to 550 ℃ at the rate of 2 ℃/min, preserving the temperature for 1 h, naturally cooling, and grinding to obtain the metal organic framework derived one-dimensional iron-based wave-absorbing material; the one-dimensional iron-based wave-absorbing material is gray black powder, and comprises iron, ferroferric oxide and ferrous oxide, wherein the mass fraction of iron element is 63.38%; the powder particles are in the form of one-dimensional beads which are cylindrical beads having a length of 2000nm and a diameter of 500 nm.
Referring to fig. 7, an XRD spectrum of the one-dimensional iron-based wave absorbing material S2 prepared in this example 2. Three distinct diffraction peaks can be seen in FIG. 7, corresponding to the (110), (200), (211) crystal planes of JCPDS number 89-7194 Fe. In combination with the ICP test results, the sample had an iron content of 63.38 wt% which was significantly different from pure iron, as indicated at 550oIron sesquioxide (Fe) under the reduction of C hydrogen2O3) In addition to reduction to the more crystalline pure iron (Fe) phase, it is possible for some of the oxidation products to be present in amorphous form.
Referring to fig. 8, in an SEM photograph of the one-dimensional iron-based wave absorbing material S2 prepared in this embodiment 2, compared with S1, the one-dimensional beads in S2 adhere to each other to form a conductive path; the particle size also changes from nanoscale to micron-scale, approximately 2000nm long and approximately 500 nm in diameter. This phenomenon may occur due to the high heat treatment temperature, which provides the material with high energy due to the high reduction temperature, resulting in an increased grain growth rate.
Referring to fig. 9, the complex permittivity and complex permeability spectrogram of the one-dimensional iron-based wave-absorbing material S2 with the filling degree of 60 wt% prepared in this example 2. Compared with S1, the complex permittivity of S2 is significantly increased, with the real part increasing from 23.72 to 77.74 of S1 and the imaginary part increasing from 5.28 to 30.00. The complex permeability also rises by a certain amount, but the overall change is not large. On one hand, the parameters are obviously changed because the components of the material are changed to a certain extent after the reduction temperature is increased, and the pure iron (Fe) phase has higher magnetic permeability and dielectric constant. On the other hand, from the appearance, the particles in the S2 are obviously interconnected to form a conductive path, so that the conductive property of the material is further improved.
Referring to fig. 10, a reflection loss curve chart of the one-dimensional iron-based wave-absorbing material S2 with a filling degree of 60 wt% prepared in this example 2. RL of S2 samples is more than-10 dB, which shows that the wave absorbing performance of the material is poor. This is because the presence of pure iron (Fe) phase and conductive path in S2 results in extremely high dielectric constant at the same filling level, which seriously affects the impedance matching capability of the material and thus the reflection loss is less expressed.
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
Claims (1)
1. A one-dimensional iron-based wave-absorbing material derived from a metal organic framework is characterized in that:
the one-dimensional iron-based wave-absorbing material is gray black powder, and comprises iron, ferroferric oxide and ferrous oxide, wherein the mass fraction of iron element is 47.3-63.79%; the particles of the gray black powder are in a one-dimensional bead shape, the beads are cylindrical beads, the length of the beads is 300-2000 nm, and the diameter of the beads is 20-1000 nm;
the preparation operation steps of the one-dimensional iron-based wave-absorbing material derived from the metal organic framework are as follows:
(1) dissolving 1.08 g of ferric chloride hexahydrate in 54 mL of N, N-dimethylformamide solution, stirring for 10 min, adding 0.88 g of terephthalic acid, and stirring for 30 min to obtain iron salt solution; dissolving 0.096 g of sodium hydroxide in 6 mL of deionized water, adding into the ferric salt solution, and carrying out solvothermal reaction at 100 ℃ for 24 h; the product was centrifuged and washed twice with N, N-dimethylformamide; drying for 1 hour in a vacuum drying oven at the temperature of 80 ℃; grinding to obtain metal organic framework powder; the metal organic framework powder is light yellow, iron is used as a central metal element, terephthalic acid is used as an organic ligand and is marked as Fe-bdc, particles of the metal organic framework powder are in a one-dimensional rod shape, the length of the rod is 1000 nm, and the diameter of the rod is 100 nm;
(2) taking 1 g of the metal organic framework powder, carrying out heat treatment in a muffle furnace under the air condition, raising the temperature to 450-650 ℃ at the speed of 2 ℃/min, preserving the heat for 4 hours, naturally cooling, and grinding to obtain metal organic framework derived iron oxide powder, wherein the metal organic framework derived iron oxide powder is red, the powder particles are rod-shaped, the rod length is 300-1000 nm, and the diameter is 20-100 nm;
(3) taking 0.5g of the metal organic framework derived iron oxide powder, reducing in a tubular furnace in a hydrogen atmosphere, heating to 350-550 ℃ at the speed of 2 ℃/min, preserving the temperature for 1 h, naturally cooling, and grinding to obtain the metal organic framework derived one-dimensional iron-based wave-absorbing material; the one-dimensional iron-based wave-absorbing material is gray black powder, and comprises iron, ferroferric oxide and ferrous oxide, wherein the mass fraction of iron element is 47.3-63.79%; the powder particles are in a one-dimensional bead shape, the bead is a cylindrical bead, the length of the bead is 300-2000 nm, and the diameter of the bead is 20-1000 nm.
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