CN113825380B - Cobalt/manganese oxide/porous graphitized carbon wave-absorbing material and preparation method thereof - Google Patents
Cobalt/manganese oxide/porous graphitized carbon wave-absorbing material and preparation method thereof Download PDFInfo
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- 239000011358 absorbing material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title description 6
- 239000010941 cobalt Substances 0.000 title description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 3
- 229910052799 carbon Inorganic materials 0.000 title description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 239000013118 MOF-74-type framework Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 23
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 22
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 17
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012153 distilled water Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 32
- 239000012265 solid product Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 238000007605 air drying Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 240000002853 Nelumbo nucifera Species 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 3
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 102000017946 PGC-1 Human genes 0.000 description 1
- 108700038399 PGC-1 Proteins 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
Abstract
The invention relates to a preparation method of Co/MnO/PGC wave absorbing material, firstly mixing cobalt chloride hexahydrate, manganese chloride tetrahydrate and absolute ethyl alcohol, stirring until the cobalt chloride hexahydrate, the manganese chloride tetrahydrate and the absolute ethyl alcohol are completely dissolved to obtain solution A; adding 2, 5-dihydroxyterephthalic acid into a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, and uniformly stirring to obtain a solution B; and (3) dropwise adding the solution A into the solution B, rapidly stirring, transferring the mixture into a reaction kettle, placing in a forced air drying oven for heating reaction, cooling to room temperature after the reaction is finished, centrifugally separating a reaction product, filtering, alternately washing with absolute ethyl alcohol and N-N dimethylformamide, drying to obtain a Co/Mn-MOF-74 precursor, and calcining the precursor under nitrogen to obtain the catalyst. The method has the advantages of simple preparation flow, easy control and low production cost, and the prepared composite material has excellent wave absorbing performance and has good application prospect in the field of electromagnetic wave absorption.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a preparation method of a cobalt/manganese oxide/porous graphitized carbon (Co/MnO/PGC) wave-absorbing material.
Background
Along with the progress of the times, the national economy and technology are developed at a high speed, and digital and high-frequency electromagnetic equipment is changed day by day, so that a large amount of electromagnetic radiation can be generated in the use process of the equipment, serious electromagnetic pollution is brought, and the health of human beings is influenced. Therefore, the development of the wave-absorbing material with strong absorption capacity and wave-absorbing frequency bandwidth has important significance.
The electromagnetic wave absorbing material is a material which can allow an electromagnetic wave incident on the surface of the wave absorbing material to enter the material, and can attenuate the incident electromagnetic wave in the material through various loss mechanisms, or can cause interference due to the generation of an optical path difference between the incident electromagnetic wave and the reflected electromagnetic wave, so that the incident electromagnetic wave and the reflected electromagnetic wave cancel each other out.
Along with the continuous research of the wave-absorbing material, four requirements of thinness, lightness, width and strength are provided for the wave-absorbing material, and the wave-absorbing material in the prior art has the problems of high density and narrow wave-absorbing frequency band and has poor electromagnetic wave absorption performance. Compared with other types of wave-absorbing materials, the carbon-based material has the advantages of large specific surface area, low density, good stability, light weight and the like, and the porous structure is beneficial to the absorption of electromagnetic waves, so that the porous carbon-based material is selected as the wave-absorbing material, and the development prospect is wider.
Disclosure of Invention
The invention aims to solve the problems of high density and narrow wave-absorbing band of the wave-absorbing material in the prior art, and provides a preparation method of a Co/MnO/PGC wave-absorbing material, which has the characteristics of simple preparation process, easy control and low production cost, light weight, low density, wide effective absorption bandwidth and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a Co/MnO/PGC wave absorbing material comprises the following steps:
(1) Adding cobalt chloride hexahydrate and manganese chloride tetrahydrate into absolute ethyl alcohol, and stirring until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A;
(2) Adding 2, 5-dihydroxyterephthalic acid into a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, and stirring and dissolving to obtain a solution B;
(3) Dropwise adding the solution A into the solution B, rapidly stirring, transferring the mixed solution to a reaction kettle after dropwise adding, placing the reaction kettle in a blast drying oven, heating to react, cooling to room temperature after the reaction is finished, taking out the reaction kettle, centrifugally separating a reaction product, filtering, alternately washing with absolute ethyl alcohol and N-N dimethylformamide to obtain a solid product, and drying to obtain a cobalt/manganese-MOF-74 (Co/Mn-MOF-74) precursor;
(4) Calcining the Co/Mn-MOF-74 precursor under nitrogen atmosphere, and finally cooling to room temperature to obtain the Co/MnO/PGC wave absorbing material.
In the step (1), the molar ratio of cobalt chloride hexahydrate to manganese chloride tetrahydrate is (1-4): 1.
Further, in the step (2), the molar ratio of the 2, 5-dihydroxyterephthalic acid to the total amount of cobalt chloride hexahydrate and manganese chloride tetrahydrate is 1:4.
In the step (2), the volume ratio of the distilled water, the absolute ethyl alcohol and the N-N dimethylformamide in the mixed solvent of the distilled water, the absolute ethyl alcohol and the N-N dimethylformamide is 1:1:1.
Further, in the step (3), the rotating speed of the rapid stirring is 400-800 r/min, and the time is 6-12 h.
In the step (3), the heating temperature is 130-160 ℃, the heating rate is 5-8 ℃/min, and the reaction time is 12h.
In the step (3), the rotational speed of centrifugal separation is 8000-10000 r/min, and the time is 5-10 min.
In the step (3), the drying temperature is 60-80 ℃ and the drying time is 12-14 h.
In the step (4), the temperature rising rate is 2-3 ℃/min, the calcining temperature is 700-800 ℃, and the calcining time is 3-4 h.
The invention has the beneficial effects that:
according to the invention, cobalt chloride hexahydrate and manganese chloride tetrahydrate are used as raw materials, 2, 5-dihydroxyterephthalic acid is used as an organic ligand, a mixed solution of distilled water, absolute ethyl alcohol and N-N dimethylformamide is used as a solvent to prepare the Co/Mn-MOF-74 precursor, and the prepared Co/Mn-MOF-74 precursor has the advantages of unique appearance, large specific surface area, simple preparation process, low cost and repeated operation. The Co/Mn-MOF-74 precursor is carbonized to obtain the Co/MnO/PGC wave absorbing material which is in a symmetrical lotus shape, has light weight and low filling quantity, and the void structure can generate a large amount of interface polarization, when the matching thickness is 2 mm, the filling quantity is 20%, the maximum reflection loss is-47.5 dB when the frequency is 15.36 GHz, the effective bandwidth is 5.7 GHz (12.3 GHz-18 GHz), and the Co/Mn-MOF-74 precursor wave absorbing material is an efficient light broadband wave absorbing material.
Drawings
FIG. 1 is an XRD pattern of the Co/Mn-MOF-74 precursor prepared in examples 1-4;
FIG. 2 is a FT-IR diagram of a Co/Mn-MOF-74 precursor prepared in examples 1-4;
FIG. 3 is an XRD pattern of the Co/MnO/PGC wave absorbing material prepared in examples 1 to 4;
FIG. 4 is an SEM image of the Co/Mn-MOF-74 precursor and Co/MnO/PGC wave absorbing material prepared in example 3;
FIG. 5 is a reflection loss curve of the Co/MnO/PGC absorbing material prepared in example 3 at a thickness of 1.0 mm-5.5 mm.
Description of the embodiments
In order to make the objects and advantages of the present invention more apparent, the technical scheme of the present invention will be specifically described with reference to the accompanying drawings and examples. It should be understood that the following text is intended to describe only one or more specific embodiments of the invention and does not limit the scope of the invention strictly as claimed.
Examples
A preparation method of a Co/MnO/PGC wave absorbing material comprises the following steps:
(1) Adding 3 mmol of cobalt chloride hexahydrate and 3 mmol of manganese chloride tetrahydrate into 10 mL absolute ethyl alcohol, and magnetically stirring for 1h until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A;
(2) Adding 1.5 mmol of 2, 5-dihydroxyterephthalic acid into a mixed solvent of 60 mL distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water, the absolute ethyl alcohol and the N-N dimethylformamide is 1:1:1), and magnetically stirring 1.5 h until the solution is uniformly dissolved to obtain a solution B;
(3) Dropwise adding the solution A into the solution B, rapidly stirring the solution A for 9 h (with the rotating speed of 500 r/min), transferring the mixed solution to a 100 mL reaction kettle after the dropwise adding is completed, placing the reaction kettle into a blast drying box, heating the reaction kettle to 140 ℃ at the heating rate of 6 ℃/min for reacting 12h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the reaction kettle, centrifugally separating reaction products, filtering, alternately washing the reaction products for 3 times by using absolute ethyl alcohol and N-N dimethylformamide to obtain solid products, and placing the solid products into a vacuum drying box at 60 ℃ for drying 24 h to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co 1Mn 1);
(4) And heating the Co/Mn-MOF-74 precursor to 700 ℃ at a speed of 2 ℃/min under nitrogen atmosphere, calcining 3 h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave absorbing material (Co/MnO/PGC-1:1).
Examples
A preparation method of a Co/MnO/PGC wave absorbing material comprises the following steps:
(1) Adding 4 mmol of cobalt chloride hexahydrate and 2 mmol of manganese chloride tetrahydrate into 10 mL absolute ethyl alcohol, and magnetically stirring for 1h until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A;
(2) Adding 1.5 mmol of 2, 5-dihydroxyterephthalic acid into a mixed solvent of 60 mL distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water, the absolute ethyl alcohol and the N-N dimethylformamide is 1:1:1), and magnetically stirring 1.5 h until the solution is uniformly dissolved to obtain a solution B;
(3) Dropwise adding the solution A into the solution B, rapidly stirring the solution A for 9 h (with the rotating speed of 500 r/min), transferring the mixed solution to a 100 mL reaction kettle after the dropwise adding is completed, placing the reaction kettle into a blast drying box, heating the reaction kettle to 140 ℃ at the speed of 6 ℃/min for reacting for 12h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the reaction kettle, centrifugally separating reaction products, filtering, alternately washing the reaction products for 3 times by using absolute ethyl alcohol and N-N dimethylformamide to obtain solid products, and placing the solid products into a vacuum drying box at 60 ℃ for drying for 24 h to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co 2Mn 1);
(4) And heating the Co/Mn-MOF-74 precursor to 700 ℃ at a speed of 2 ℃/min under a nitrogen atmosphere, calcining 3 h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave absorbing material (Co/MnO/PGC-2:1).
Examples
A preparation method of a Co/MnO/PGC wave absorbing material comprises the following steps:
(1) Adding 4.5 mmol of cobalt chloride hexahydrate and 1.5 mmol of manganese chloride tetrahydrate into 10 mL absolute ethyl alcohol, and magnetically stirring for 1h to completely dissolve to obtain a solution A;
(2) Adding 1.5 mmol of 2, 5-dihydroxyterephthalic acid into a mixed solvent of 60 mL distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water, the absolute ethyl alcohol and the N-N dimethylformamide is 1:1:1), and magnetically stirring 1.5 h until the solution is uniformly dissolved to obtain a solution B;
(3) Dropwise adding the solution A into the solution B, rapidly stirring the solution A for 9 h (the rotating speed is 500 r/min), transferring the mixed solution to a 100 mL reaction kettle after the dropwise adding is completed, placing the reaction kettle into a blast drying box, heating to 140 ℃ at the speed of 6 ℃/min, reacting for 12h, cooling to room temperature after the reaction is finished, taking out the reaction kettle, centrifugally separating reaction products, filtering, alternately washing the reaction products for 3 times by using absolute ethyl alcohol and N-N dimethylformamide to obtain solid products, and drying for 24 h in a vacuum drying box at 60 ℃ to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co 3Mn 1);
(4) And heating the Co/Mn-MOF-74 precursor to 700 ℃ at a speed of 2 ℃/min under a nitrogen atmosphere, calcining 3 h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave absorbing material (Co/MnO/PGC-3:1).
Examples
A preparation method of a Co/MnO/PGC wave absorbing material comprises the following steps:
(1) Adding 4.8 mmol of cobalt chloride hexahydrate and 1.2 mmol of manganese chloride tetrahydrate into 10 mL absolute ethyl alcohol, and magnetically stirring for 1h to completely dissolve to obtain a solution A;
(2) Adding 1.5 mmol of 2, 5-dihydroxyterephthalic acid into a mixed solvent of 60 mL distilled water, absolute ethyl alcohol and N-N dimethylformamide (the volume ratio of the distilled water, the absolute ethyl alcohol and the N-N dimethylformamide is 1:1:1), and magnetically stirring 1.5 h until the solution is uniformly dissolved to obtain a solution B;
(3) Dropwise adding the solution A into the solution B, rapidly stirring the solution A for 9 h (with the rotating speed of 500 r/min), transferring the mixed solution to a 100 mL reaction kettle after the dropwise adding is completed, placing the reaction kettle into a blast drying box, heating the reaction kettle to 140 ℃ at the speed of 6 ℃/min for reacting for 12h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the reaction kettle, centrifugally separating reaction products, filtering, alternately washing the reaction products for 3 times by using absolute ethyl alcohol and N-N dimethylformamide to obtain solid products, and placing the solid products into a vacuum drying box at 60 ℃ for drying for 24 h to obtain a Co/Mn-MOF-74 precursor (MOF-74-Co 4Mn 1);
(4) And heating the Co/Mn-MOF-74 precursor to 700 ℃ at a speed of 2 ℃/min under nitrogen atmosphere, calcining 3 h, and finally cooling to room temperature to obtain the Co/MnO/PGC wave absorbing material (Co/MnO/PGC-4:1).
Phase structure analysis was performed on the precursors and the wave-absorbing materials of examples 1 to 4 using an X-ray diffractometer (XRD) and a Fourier transform infrared spectrometer (FT-IR); the microstructures of the precursors and the composite materials of examples 1 to 4 were analyzed by a Scanning Electron Microscope (SEM), and electromagnetic parameters of the samples were analyzed by means of a Vector Network Analyzer (VNA), thereby calculating the wave absorbing performance. The test results are shown in FIGS. 1-5.
FIG. 1 shows XRD patterns of the Co/Mn-MOF-74 precursor prepared in examples 1-4, and it can be seen that the Co/Mn-MOF-74 precursor prepared in examples 1-4 of the present invention has no impurity phase formation, sharp peak shape, good crystallinity, and one diffraction peak at 2θ=6.7°, 11.7 °, which correspond to crystal planes (110) and (300), respectively, and the result is identical to that of the standard card of the Co/Mn-related metal-organic framework.
FIG. 2 is a FT-IR chart of the Co/Mn-MOF-74 precursor prepared in examples 1-4, from which it can be seen that Co/MnO/PGC prepared in different proportions are each 3430cm -1 A distinct O-H bond formed by residual water molecules; at 2917cm -1 The weak peak at which corresponds to stretching of the C-H bond; 1629cm -1 The peak appearing at this point is due to a c=c double bond; 1078cm -1 The peak at the point is the bending vibration peak of the C-H bond; 572cm -1 The characteristic absorption peak at the site is a vibration peak of Mn-O bond. This result is consistent with the XRD results described above, demonstrating that the Co/MnO/PGC composite material has been successfully synthesized.
FIG. 3 shows XRD patterns of Co/MnO/PGC absorbing materials prepared in examples 1-4, in which Co/MnO/PGC prepared in different cobalt-manganese ratios have the same diffraction peaks, one diffraction peak at 2θ=44.2°, 51.5 ° and 75.9 ° respectively, corresponding to (111), (200) and (220) crystal planes (JCPDS No. 15-0806) of Co, respectively, indicating Co 2+ Is reduced to metallic Co during calcination; 2θ=34.91 °, 40.5 °, 58.7 °, 70.2 °, 73.8 ° have a distinct diffraction peak, respectively, corresponding to the (111), (200), (220), (311), (222) crystal planes of MnO (JCPDS No. 07-0203), respectively, and other miscellaneous peaks are absent. As the Co content increases, the diffraction peak of MnO becomes weaker.
FIG. 4 is an SEM image of the Co/Mn-MOF-74 precursor and Co/MnO/PGC absorbing material prepared in example 3, wherein FIG. 4 (a) and FIG. 4 (b) correspond to the SEM image of the Co/Mn-MOF-74 precursor, and FIG. 4 (c) and FIG. 4 (d) correspond to the SEM image of Co/MnO/PGC. As can be seen from the figure, the Co/Mn-MOF-74 precursor prepared by adopting the 2, 5-dihydroxyterephthalic acid as an organic ligand has similar shapes, is in a symmetrical lotus shape, and has smooth surface and relatively uniform distribution. The Co/MnO/PGC composite material obtained by carbonization still maintains the symmetrical lotus shape of the precursor, but slightly shrinks in size and slightly collapses in surface.
FIG. 5 is a graph showing the reflection loss of the Co/MnO/PGC absorbing material prepared in example 3 at a thickness of 1.0 mm-5.5 mm, and it can be seen from the graph that when the matching thickness is 2. 2 mm, the maximum reflection loss is-47.5 dB at a frequency of 15.36 GHz and the effective bandwidth is 5.7 GHz (12.3 GHz-18 GHz), the absorbing material has excellent electromagnetic wave absorption performance, and meets the requirements of 'thin, light, wide and strong' of the absorbing material.
While the embodiments of the present invention have been described in detail with reference to the examples, the present invention is not limited to the above embodiments, and it will be apparent to those skilled in the art that various equivalent changes and substitutions can be made therein without departing from the principles of the present invention, and such equivalent changes and substitutions should also be considered to be within the scope of the present invention.
Claims (7)
1. The preparation method of the Co/MnO/PGC wave absorbing material is characterized by comprising the following steps:
(1) Adding cobalt chloride hexahydrate and manganese chloride tetrahydrate into absolute ethyl alcohol, and stirring until the cobalt chloride hexahydrate and the manganese chloride tetrahydrate are completely dissolved to obtain a solution A;
(2) Adding 2, 5-dihydroxyterephthalic acid into a mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, and stirring and dissolving to obtain a solution B;
(3) Dropwise adding the solution A into the solution B, rapidly stirring, transferring the mixed solution to a reaction kettle after dropwise adding, placing the reaction kettle in a blast drying oven, heating to 130-160 ℃, cooling to room temperature after the reaction is finished, centrifugally separating a reaction product, filtering, alternately washing with absolute ethyl alcohol and N-N dimethylformamide to obtain a solid product, and drying to obtain a Co/Mn-MOF-74 precursor;
(4) Calcining the Co/Mn-MOF-74 precursor in a nitrogen atmosphere to obtain a Co/MnO/PGC wave-absorbing material;
in the step (1), the mol ratio of cobalt chloride hexahydrate to manganese chloride tetrahydrate is (1-4): 1;
in the step (2), in the mixed solvent of distilled water, absolute ethyl alcohol and N-N dimethylformamide, the volume ratio of the distilled water, the absolute ethyl alcohol and the N-N dimethylformamide is 1:1:1.
2. The method for producing a Co/MnO/PGC wave absorbing material according to claim 1, wherein in the step (2), the molar ratio of the 2, 5-dihydroxyterephthalic acid to the total amount of cobalt chloride hexahydrate and manganese chloride tetrahydrate is 1:4.
3. The method for preparing a Co/MnO/PGC wave absorbing material according to claim 1, wherein in the step (3), the rotation speed of the rapid stirring is 400-800 r/min, and the time is 6-12 hours.
4. The method for preparing a Co/MnO/PGC absorbing material according to claim 1, wherein in the step (3), the heating rate is 5-8 ℃/min, and the reaction time is 12h.
5. The method for producing Co/MnO/PGC absorbing material according to claim 1, wherein in the step (3), the rotational speed of the centrifugal separation is 8000 to 10000 r/min for 5 to 10 min.
6. The method for producing a Co/MnO/PGC absorbing material according to claim 1, wherein in the step (3), the drying temperature is 60 to 80℃and the time is 12 to 14 hours.
7. The method of producing a Co/MnO/PGC absorbing material according to any one of claims 1 to 6, wherein in the step (4), the heating rate is 2 to 3 ℃/min, the calcination temperature is 700 to 800 ℃ and the calcination time is 3 to 4 hours.
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