CN112980390B - Preparation method of bimetal organic framework derived magnetic carbon composite wave-absorbing material - Google Patents
Preparation method of bimetal organic framework derived magnetic carbon composite wave-absorbing material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000011358 absorbing material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013384 organic framework Substances 0.000 title claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 241000219991 Lythraceae Species 0.000 claims abstract description 5
- 235000014360 Punica granatum Nutrition 0.000 claims abstract description 5
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims description 33
- 239000002244 precipitate Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 28
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 16
- 150000003751 zinc Chemical class 0.000 abstract description 15
- 229940044631 ferric chloride hexahydrate Drugs 0.000 abstract description 9
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 abstract description 8
- 239000011592 zinc chloride Substances 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 7
- 150000002505 iron Chemical class 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000013110 organic ligand Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- 238000012360 testing method Methods 0.000 description 13
- 230000005415 magnetization Effects 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- 239000011701 zinc Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
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- 230000033228 biological regulation Effects 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Abstract
The invention discloses a bimetal organic frameworks (MOFs) derived magnetic carbon composite wave-absorbing material and a preparation method thereof. The iron-based bi-metal MOFs derived magnetic carbon composite wave-absorbing material is prepared by a two-step solvothermal and thermal pyrolysis method by taking graphene oxide as a template, ferric chloride hexahydrate and zinc chloride as metal salt precursors, taking terephthalic acid as an organic ligand and taking N, N-dimethylformamide as a solvent. The preparation method is green and environment-friendly, does not generate any toxic byproducts, and has simple preparation process. The prepared composite material enables the shape of the carbon framework to be gradually changed from a traditional regular octahedron to a pomegranate shape by simply changing the mole ratio of iron salt and zinc salt in the precursor, and meanwhile, the matching thickness is changed, so that strong absorption and wide bandwidth can be realized, the Ku wave band is almost completely covered by effective absorption, and the composite material has important application value in the fields of electromagnetic absorption and electromagnetic shielding.
Description
Technical Field
The invention belongs to the technical field of electromagnetic composite materials, and particularly relates to a preparation method of a bimetal organic framework derived magnetic carbon composite wave-absorbing material.
Technical Field
Since the 21 st century, technological progress led to rapid changes in human life style, and particularly rapid development and wide application of various electronic and electric devices, so that human production efficiency is higher and life experience is more convenient and comfortable. However, the application of more and more electronic and electric equipment brings potential hazard, and electromagnetic radiation and interference generated by the electronic and electric equipment are intangibly destroyed in the production and living environment of human beings. In addition, with the change of international strategic environment, stealth technology has become an important embodiment of military strength angle of each country. Therefore, the development of high-performance wave-absorbing materials to suppress electromagnetic radiation pollution and enhance radar stealth has important significance in the military and civilian fields.
The carbon material has the advantages of lower density, good chemical stability, excellent electric conductivity and the like, so that the carbon material is a potential wave-absorbing material. Reduced Graphene Oxide (RGO) is a novel two-dimensional carbon nanomaterial that is generally prepared from natural graphite by chemical oxidation-reduction. RGO has good application prospect in the field of electromagnetic wave absorbing materials due to a unique two-dimensional layered structure, good chemical stability and excellent dielectric loss capability. However, a single RGO has the disadvantage of impedance mismatch and has poor electromagnetic wave attenuation capability, so that the application of RGO in the field of electromagnetic wave absorption is limited, and it is difficult to satisfy the requirements of commercial applications (reflection loss value below-10 dB).
Metal Organic Frameworks (MOFs) are a class of crystalline porous materials with periodic network structures formed by self-assembled interconnection of inorganic metal centers (metal ions or metal clusters) and bridged organic ligands. Due to the excellent characteristics of structural diversity, porosity, tailorability, ultra-high specific surface area and the like, MOFs have wide application prospects in the research fields of catalysis, energy storage, separation and the like. In recent years, it has been found that magnetic metal/carbon composites can be generated in situ by pyrolysis in an inert atmosphere using MOFs as precursors. Iron and its oxide/porous carbon nano composite material can be produced when iron-based MOFs are pyrolyzed at high temperature, and the iron-based MOFs have good magnetic loss, dielectric loss characteristics and unique pore structures, can effectively attenuate incident electromagnetic waves through mechanisms such as synergism and interfacial polarization, and are therefore potential microwave absorbing materials with excellent performance. However, there are few reports of iron-based bimetallic MOFs-derived magnetic carbon composite wave-absorbing materials.
According to the invention, graphene Oxide (GO) is used as a template, firstly, solvothermal reaction is adopted to grow (Fe, zn) bimetallic MOFs on the surface of the graphene oxide, and then, the magnetic carbon composite wave-absorbing material is prepared by pyrolysis in an argon atmosphere. The morphology of the carbon framework is gradually changed from the traditional regular octahedron to the pomegranate shape by simply changing the mole ratio of the iron salt to the zinc salt in the precursor, and the static magnetic property and the electromagnetic parameter of the composite material are regulated, so that the effective regulation and control of the wave absorbing property of the composite material are realized.
Disclosure of Invention
The invention aims to provide a bimetal-organic framework derived magnetic carbon composite wave-absorbing material and a preparation method thereof, and the composite material has the characteristics of controllable microcosmic appearance, high microwave absorption intensity, wide absorption frequency band, thin matching thickness, easy regulation and control of absorption wave bands and the like, and is simple in preparation process and environment-friendly.
The invention is realized by the following technical scheme:
a bimetal MOFs derived magnetic carbon composite wave-absorbing material is composed of a porous carbon framework with special appearance (regular octahedron and pomegranate shape) of fold RGO entanglement.
A bimetal MOFs derived magnetic carbon composite wave-absorbing material comprises the following steps:
(1) Taking 1 beaker with 150mL, adding 80mL of N, N-Dimethylformamide (DMF), adding 80mg of graphite oxide while stirring, and stirring for 0.5h after ultrasonic treatment for 1.5h to prepare GO dispersion with the concentration of 1 mg/mL;
(2) Adding a certain mass of ferric chloride hexahydrate (FeCl) into the GO dispersion liquid 3 ·6H 2 O) and zinc chloride (ZnCl) 2 ) Stirring vigorously to dissolve completely, and controlling Fe 3+ /Zn 2+ The molar ratio is 1:0, 1:0.5, 1:1, 1:2, 1:3, 1:4;
(3) 1.2227g of terephthalic acid (H) was added to the mixed dispersion obtained above 2 BDC) is vigorously stirred until the BDC is completely dissolved, and stirring is continued for 0.5h;
(4) Transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24 hours at 110 ℃;
(5) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
(6) Transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours to constant weight;
(7) And (3) carrying out high-temperature annealing treatment on the dried precipitate in a tubular furnace filled with argon protective atmosphere, wherein the temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the invention adopts the two-step method of solvothermal and thermal pyrolysis to prepare the bimetal MOFs-derived magnetic carbon composite wave-absorbing material, has simple and convenient operation, is green and safe, and does not generate any toxic and harmful substances.
2. According to the invention, the morphology of the carbon framework is gradually changed from the traditional regular octahedron to the pomegranate shape by simply changing the mole ratio of the iron salt to the zinc salt in the precursor, and the static magnetic property and the electromagnetic parameter of the composite material are regulated, so that the effective regulation and control of the wave absorbing property of the composite material are realized.
3. The magnetic carbon composite material prepared by the invention has excellent wave absorbing performance, and has the characteristics of low filling ratio, thin matching thickness, large absorption strength, wide absorption frequency band, easy regulation and control of absorption performance and the like. At a thickness of 2.76mm, the maximum absorption intensity can reach-79.0 dB, and at a thickness of 1.82mm, the microwave absorption intensity in the range of 12.2-18.0GHz is below-10 dB, the effective absorption bandwidth reaches 5.8GHz, and the Ku wave band (12.0-18.0 GHz) is almost completely covered; the electromagnetic waves of different wave bands can be effectively absorbed by adjusting the molar ratio and the matching thickness of the ferric salt and the zinc salt in the precursor.
4. The magnetic carbon composite wave-absorbing material prepared by the invention realizes effective attenuation of electromagnetic waves through the synergistic effect of physical mechanisms such as optimized impedance matching, interface polarization, dipole polarization, magnetic resonance loss, eddy current loss and the like.
Drawings
FIG. 1 is an XRD spectrum of the product of examples 1,2, 3, 4, 5, 6;
FIG. 2 is XPS spectrum of product S4 from example 4;
FIG. 3 is XPS C1S spectrum of product S4 in example 4;
FIG. 4 is XPS O1S spectrum of product S4 in example 4;
FIG. 5 is XPS Fe 2p spectrum of product S4 in example 4;
FIG. 6 is XPS Zn 2p spectrum of product S4 in example 4;
FIG. 7 is an SEM photograph of the product S1 of example 1;
FIG. 8 is an SEM photograph of the product S2 of example 2;
FIG. 9 is an SEM photograph of the product S3 of example 3;
FIG. 10 is an SEM photograph of the product S4 of example 4;
FIG. 11 is an SEM photograph of the product S5 of example 5;
FIG. 12 is an SEM photograph of the product S6 of example 6;
FIG. 13 is a hysteresis loop diagram (upper left corner is a partial enlarged view of hysteresis loop) of the products in examples 1,2, 3, 4, 5, 6;
FIG. 14 is a plot of reflection loss of product S1 as a function of frequency in example 1;
FIG. 15 is a plot of reflection loss of product S2 as a function of frequency in example 2;
FIG. 16 is a plot of reflection loss of product S3 as a function of frequency in example 3;
FIG. 17 is a plot of reflection loss of product S4 as a function of frequency for example 4;
FIG. 18 is a graph showing the reflection loss of the product S5 in example 5 as a function of frequency;
fig. 19 is a graph showing the reflection loss of the product S6 in example 6 with respect to frequency.
Detailed description of the preferred embodiments
The invention will now be further described with reference to examples and figures:
example 1
(1) Taking 1 150mL beaker, adding 80mL DMF, adding 80mg graphite oxide while stirring, stirring for 0.5h after ultrasonic treatment for 1.5h, and preparing GO dispersion with the concentration of 1 mg/mL;
(2) 1.989g FeCl was added to the GO dispersion obtained above 3 ·6H 2 Stirring vigorously to dissolve O completely;
(3) Adding 1.2227g H to the above obtained mixed dispersion 2 After BDC is vigorously stirred to be completely dissolved, finally, the BDC is vigorously stirred for 0.5h;
(4) Transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24 hours at 110 ℃;
(5) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
(6) Transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours to constant weight;
(7) And (3) carrying out high-temperature annealing treatment on the dried precipitate in a tubular furnace filled with argon protective atmosphere, wherein the temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature and is marked as S1.
XRD patterns of the product of example 1 are shown in fig. 1,2θ=18.4°,30.1 °,35.5 °,43.2 °,53.6 °,57.0 ° and 62.6 ° with Fe 3 O 4 The positions of the standard cards (JCPDS No. 75-1609) (111), (220), (311), (400), (422), (511) and (440) crystal faces are consistent, and other characteristic peaks are not seen in the figure, which shows that Fe is prepared under the experimental condition 3 O 4 . Fig. 7 is an SEM photograph of example 1, from which it can be seen that the carbon framework morphology exhibits a uniform regular octahedral morphology, and that the carbon framework adheres to the wrinkled RGO sheets. The hysteresis loop diagram of the product of example 1 is shown in FIG. 13, and it can be seen from the partial enlargement of the low-field hysteresis loop that the saturation magnetization is 47.8emu/g. The powder product of example 1 and paraffin wax were mixed in a mass ratio of 2:8, pressing into a coaxial sample with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die, testing electromagnetic parameters by using an AV3629D vector network analyzer, calculating to obtain the wave absorbing performance, and testing the frequency range of 2-18GHz. The reflection loss versus frequency curve of sample S1 is shown in FIG. 14, and the maximum absorption strength reaches-10.0 dB at 12.0GHz when the matching thickness is 2.5 mm.
Example 2
(1) Taking 1 150mL beaker, adding 80mL DMF, adding 80mg graphite oxide while stirring, stirring for 0.5h after ultrasonic treatment for 1.5h, and preparing GO dispersion with the concentration of 1 mg/mL;
(2) 1.3271g FeCl was added to the GO dispersion obtained above 3 ·6H 2 O and 0.3339g ZnCl 2 Stirring vigorously to dissolve completely;
(3) Adding 1.2227g H to the above obtained mixed dispersion 2 After BDC is vigorously stirred to be completely dissolved, finally, the BDC is vigorously stirred for 0.5h;
(4) Transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24 hours at 110 ℃;
(5) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
(6) Transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours to constant weight;
(7) And (3) carrying out high-temperature annealing treatment on the dried precipitate in a tubular furnace filled with argon protective atmosphere, wherein the temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature and is marked as S2.
XRD patterns of the product of example 2 are shown in fig. 1,2θ=18.4°,30.1 °,35.5 °,43.2 °,53.6 °,57.0 ° and 62.6 ° with Fe 3 O 4 The positions of the standard cards (JCPDS No. 75-1609) (111), (220), (311), (400), (422), (511) and (440) crystal faces are consistent, and other characteristic peaks are not seen in the figure, which shows that Fe is prepared under the experimental condition 3 O 4 . SEM pictures are shown in fig. 8, from which it can be seen that the carbon framework exhibits a non-uniform regular octahedral morphology, indicating that the morphology of the carbon framework can be altered by the addition of zinc salt and that the wrinkled RGO sheets entangle the carbon framework. The hysteresis loop diagram of the product of example 2 is shown in fig. 13, and it can be seen from the partial enlargement of the low field hysteresis loop that the saturation magnetization is 45.8emu/g, and that the addition of zinc salt was found to reduce the saturation magnetization of the system. The powder product of example 2 and paraffin wax were mixed in a mass ratio of 2:8, pressing into a coaxial sample with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die, testing electromagnetic parameters by using an AV3629D vector network analyzer, calculating to obtain the wave absorbing performance, and testing the frequency range of 2-18GHz. As shown in FIG. 15, the reflection loss of sample S2 varies with frequency, and is maximum at 8.9GHz when the matching thickness is 2.5mmThe absorption strength reaches-16.4 dB.
Example 3
(1) Taking 1 150mL beaker, adding 80mL DMF, adding 80mg graphite oxide while stirring, stirring for 0.5h after ultrasonic treatment for 1.5h, and preparing GO dispersion with the concentration of 1 mg/mL;
(2) 0.9947g FeCl was added to the GO dispersion obtained above 3 ·6H 2 O and 0.5016g ZnCl 2 Stirring vigorously to dissolve completely;
(3) Adding 1.2227g H to the above obtained mixed dispersion 2 After BDC is vigorously stirred to be completely dissolved, finally, the BDC is vigorously stirred for 0.5h;
(4) Transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24 hours at 110 ℃;
(5) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
(6) Transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours to constant weight;
(7) And (3) carrying out high-temperature annealing treatment on the dried precipitate in a tubular furnace filled with argon protective atmosphere, wherein the temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature and is marked as S3.
XRD patterns of the product of example 3 are shown in fig. 1,2θ=18.4°,30.1 °,35.5 °,43.2 °,53.6 °,57.0 ° and 62.6 ° with Fe 3 O 4 The positions of the standard cards (JCPDS No. 75-1609) (111), (220), (311), (400), (422), (511) and (440) crystal faces are consistent, and other characteristic peaks are not seen in the figure, which shows that Fe is prepared under the experimental condition 3 O 4 . SEM photographs are shown in fig. 9, and it can be seen from the figures that the carbon framework presents a non-uniform regular octahedral shape, which shows that changing the molar ratio of iron salt to zinc salt can regulate the morphology of the carbon framework, and the wrinkled RGO sheets intertwine the carbon framework. The hysteresis loop diagram of the product of example 3 is shown in fig. 13, and as can be seen from the partial enlargement of the low field hysteresis loop, the saturation magnetization is 45.4emu/g, and the added zinc salt is found to reduce the saturation magnetization of the system. Will be implementedThe powder product and paraffin wax in example 3 were mixed in a mass ratio of 2:8, pressing into a coaxial sample with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die, testing electromagnetic parameters by using an AV3629D vector network analyzer, calculating to obtain the wave absorbing performance, and testing the frequency range of 2-18GHz. The reflection loss versus frequency curve of sample S3 is shown in FIG. 16, and the maximum absorption strength reaches-11.6 dB at 6.9GHz when the matching thickness is 3.5 mm.
Example 4
(1) Taking 1 150mL beaker, adding 80mL DMF, adding 80mg graphite oxide while stirring, stirring for 0.5h after ultrasonic treatment for 1.5h, and preparing GO dispersion with the concentration of 1 mg/mL;
(2) 0.6622g FeCl was added to the GO dispersion 3 ·6H 2 O and 0.6693g ZnCl 2 Stirring vigorously to dissolve completely;
(3) Adding 1.2227g H to the above obtained dispersion 2 After BDC is vigorously stirred to be completely dissolved, finally, the BDC is vigorously stirred for 0.5h;
(4) Transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24 hours at 110 ℃;
(5) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
(6) Transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours;
(7) And (3) carrying out high-temperature heat treatment on the dried precipitate in a tubular furnace filled with argon, wherein the temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature and is marked as S4.
XRD patterns of the product of example 4 are shown in fig. 1,2θ=18.4°,30.1 °,35.5 °,43.2 °,53.6 °,57.0 ° and 62.6 ° with Fe 3 O 4 The positions of the standard cards (JCPDS No. 75-1609) (111), (220), (311), (400), (422), (511) and (440) crystal faces are consistent, and other characteristic peaks are not seen in the figure, which shows that Fe is prepared under the experimental condition 3 O 4 . Wherein FIG. 2 is Fe 3 O 4 XPS Total of the/C/RGO composite MaterialThe spectrum shows that the sample contains C, O, fe and Zn elements, and the types of the elements are consistent with those of the prepared compound, and the appearance of the Zn elements shows that the surface layer of the sample can detect a small amount of Zn. FIG. 3 shows a C1s spectrum in which the peak at 284.7eV corresponds to the C-C/C=C bond, the peak at 285.7eV corresponds to the C=O bond, and the peak at 288.5eV corresponds to the C-OH bond. FIG. 4 shows the spectra of O1s, corresponding to the C-O, fe-O-C and Fe-O bonds, respectively. FIG. 5 shows a spectrum of Fe 2p, wherein peaks at 712.7eV and 710.9eV correspond to Fe 2p 3/2 Peak at 724.9eV corresponds to Fe 2p 1/2 Peaks at 732.5eV and 718.5eV correspond to satellite peaks. FIG. 6 shows a Zn 2p spectrum in which peaks at 1021.3eV and 1044.0eV correspond to Zn 2p, respectively 3/2 And Zn 2p 1/2 . SEM photographs are shown in fig. 10, from which it can be seen that the carbon framework exhibits a non-uniform regular octahedron and an irregular polyhedral shape, indicating that changing the molar ratio of iron salt to zinc salt can regulate the morphology of the carbon framework, and the wrinkled RGO sheets intertwine the carbon framework. The hysteresis loop diagram of the product of example 4 is shown in fig. 13, and it can be seen from the partial enlargement of the low field hysteresis loop that the saturation magnetization is 45.0emu/g, and that the addition of zinc salt was found to reduce the saturation magnetization of the system. The powder product of example 4 and paraffin wax were mixed in a mass ratio of 2:8, pressing into a coaxial sample with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die, testing electromagnetic parameters by using an AV3629D vector network analyzer, calculating to obtain the wave absorbing performance, and testing the frequency range of 2-18GHz. As shown in FIG. 17, the reflection loss of sample S4 varies with frequency, the maximum absorption intensity reaches-79.0 dB at 9.6GHz when the matching thickness is 2.76mm, the microwave absorption intensity is below-10 dB in the range of 12.2-18.0GHz when the matching thickness is 1.82mm, and the maximum absorption bandwidth of the sample is 5.8GHz.
Example 5
(1) Taking 1 150mL beaker, adding 80mL DMF, adding 80mg graphite oxide while stirring, stirring for 0.5h after ultrasonic treatment for 1.5h, and preparing GO dispersion with the concentration of 1 mg/mL;
(2) 0.4974g FeCl was added to the GO dispersion obtained above 3 ·6H 2 O and 0.7523g ZnCl 2 Stirring vigorously to dissolve completely;
(3) Adding 1.2227g H to the above obtained mixed dispersion 2 After BDC is vigorously stirred to be completely dissolved, finally, the BDC is vigorously stirred for 0.5h;
(4) Transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24 hours at 110 ℃;
(5) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
(6) Transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours to constant weight;
(7) And (3) carrying out high-temperature annealing treatment on the dried precipitate in a tubular furnace filled with argon protective atmosphere, wherein the temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature and is marked as S5.
XRD patterns of the product of example 5 are shown in fig. 1,2θ=18.4°,30.1 °,35.5 °,43.2 °,53.6 °,57.0 ° and 62.6 ° with Fe 3 O 4 The positions of the standard cards (JCPDS No. 75-1609) (111), (220), (311), (400), (422), (511) and (440) crystal faces are consistent, and other characteristic peaks are not seen in the figure, which shows that Fe is prepared under the experimental condition 3 O 4 . SEM pictures are shown in fig. 11, from which it can be seen that the carbon framework presents a garnet-like morphology. It was found that when the molar ratio of iron and zinc salts was 1:3, the carbon framework completely becomes uniform garnet shape. It can also be seen that the wrinkled RGO sheets entangle the carbon framework. The hysteresis loop diagram of the product of example 5 is shown in fig. 13, and it can be seen from the partial enlargement of the low field hysteresis loop that the saturation magnetization is 44.0emu/g, and that the addition of zinc salt was found to reduce the saturation magnetization of the system. The powder product of example 5 and paraffin wax were mixed in a mass ratio of 2:8, pressing into a coaxial sample with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die, testing electromagnetic parameters by using an AV3629D vector network analyzer, calculating to obtain the wave absorbing performance, and testing the frequency range of 2-18GHz. The reflection loss of sample S5 was plotted against frequency as shown in FIG. 18, and the maximum absorption intensity reached-16.2 dB at 14.8GHz with a matching thickness of 1.6mm, at the same matching thickness,the microwave absorption intensity is below-10 dB in the range of 12.7-18.0GHz, and the sample has the maximum absorption bandwidth of 5.3GHz.
Example 6
(1) Taking 1 150mL beaker, adding 80mL DMF, adding 80mg graphite oxide while stirring, stirring for 0.5h after ultrasonic treatment for 1.5h, and preparing GO dispersion with the concentration of 1 mg/mL;
(2) 0.3978g FeCl was added to the GO dispersion obtained above 3 ·6H 2 O and 0.8027g ZnCl 2 Stirring vigorously to dissolve completely;
(3) Adding 1.2227g H to the above obtained mixed dispersion 2 After BDC is vigorously stirred to be completely dissolved, finally, the BDC is vigorously stirred for 0.5h;
(4) Transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24 hours at 110 ℃;
(5) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
(6) Transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours to constant weight;
(7) And (3) carrying out high-temperature annealing treatment on the dried precipitate in a tubular furnace filled with argon protective atmosphere, wherein the temperature is 600 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature and is marked as S6.
The XRD patterns of the product of example 6 are shown in fig. 1,2θ=18.4°,30.1 °,35.5 °,43.2 °,53.6 °,57.0 ° and 62.6 ° with Fe 3 O 4 The positions of the standard cards (JCPDS No. 75-1609) (111), (220), (311), (400), (422), (511) and (440) crystal faces are consistent, and other characteristic peaks are not seen in the figure, which shows that Fe is prepared under the experimental condition 3 O 4 . SEM pictures are shown in fig. 12, from which it can be seen that the carbon framework presents a garnet-like morphology. It was found that as the zinc salt increased to a certain level, the further increase had little effect on the morphology of the carbon framework and the wrinkled RGO sheets entangled the carbon framework. The hysteresis loop diagram of the product of example 6 is shown in FIG. 13, which is a close-up view of the low-field hysteresis loop, showing that the saturation magnetization is strongThe degree was 43.6emu/g and the more zinc salt added the lower the saturation magnetization of the system was found. The powder product of example 6 and paraffin wax were mixed in a mass ratio of 2:8, pressing into a coaxial sample with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die, testing electromagnetic parameters by using an AV3629D vector network analyzer, calculating to obtain the wave absorbing performance, and testing the frequency range of 2-18GHz. As shown in FIG. 19, the reflection loss of the sample S6 varies with frequency, when the matching thickness is 1.6mm, the maximum absorption intensity reaches-18.6 dB at 14.2GHz, and when the matching thickness is the same, the microwave absorption intensity is below-10 dB within the range of 12.2-18.0GHz, and the effective absorption bandwidth reaches 5.8GHz.
As shown by the test results of the embodiment, the bimetal MOFs derived magnetic carbon composite wave-absorbing material is obtained by a solvothermal and pyrolysis two-step method, the method is simple to operate, safe and green, no toxic or harmful substances are generated, the electromagnetic wave absorption performance of the composite material is excellent, the maximum absorption intensity of a sample S4 reaches 79.0dB, the maximum effective absorption bandwidth reaches 5.8GHz, and the Ku wave band is almost completely covered; the electromagnetic waves of different wave bands can be effectively absorbed by adjusting the molar ratio and the matching thickness of the ferric salt and the zinc salt in the precursor. Therefore, the iron-based bimetallic MOFs-derived magnetic carbon composite material is an ideal wave-absorbing material.
Claims (3)
1. A preparation method of a bimetal organic framework derived magnetic carbon composite wave-absorbing material is characterized by comprising the following steps of: the composite material consists of a porous carbon framework formed by winding wrinkled reduced graphene oxide into a pomegranate shape;
the composite wave-absorbing material is prepared by the following method:
taking 1 beaker with 150mL, adding 80mLN of N-dimethylformamide, adding 80mg of graphite oxide while stirring, and stirring for 0.5h after ultrasonic treatment for 1.5h to prepare GO dispersion with the concentration of 1 mg/mL;
0.4974g FeCl was added to the GO dispersion obtained above 3 ·6H 2 O and 0.7523g ZnCl 2 Stirring vigorously to dissolve completely; or adding 0.3978g FeCl into the GO dispersion 3 ·6H 2 O and 0.8027g ZnCl 2 Intense stirringUntil completely dissolved;
1.2227g of terephthalic acid is added into the obtained mixed dispersion liquid and stirred vigorously until the terephthalic acid is completely dissolved, and then stirring is continued for 0.5h;
transferring the mixed dispersion liquid into an autoclave with a polytetrafluoroethylene lining and a volume of 100mL, and performing solvothermal reaction for 24h at 110 ℃;
after the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with DMF and absolute ethyl alcohol for a plurality of times, and collecting precipitate;
transferring the washed precipitate to a vacuum freeze dryer, and drying for 24 hours to constant weight;
and (3) carrying out high-temperature annealing treatment on the dried precipitate in a tubular furnace filled with argon protective atmosphere, wherein the temperature is 600 ℃, the heating rate is 5 ℃ per minute, the heat preservation time is 2 hours, and the final product is obtained after cooling to room temperature.
2. The preparation method of the bimetal MOFs-derived magnetic carbon composite wave-absorbing material is characterized by comprising the following steps of: and (3) after the solvothermal reaction in the step (5) is finished and cooled to room temperature, repeatedly centrifuging and washing with DMF to obtain a precipitate, and repeatedly centrifuging and washing with absolute ethyl alcohol to obtain the precipitate.
3. An iron-based bimetallic MOFs-derived magnetic carbon composite wave-absorbing material prepared by the preparation method of claim 1 or 2.
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