CN113088252A - Iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and preparation method thereof - Google Patents
Iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a trimetal-organic framework (FeCoNi-MOFs) derived iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and a preparation method thereof. The iron-cobalt-nickel alloy/carbon/graphene composite wave-absorbing material is prepared by using ferric nitrate nonahydrate, cobalt nitrate hexahydrate and nickel nitrate hexahydrate as metal salts, trimesic acid as an organic ligand and N, N-dimethylformamide, deionized water and ethanol as a mixed solvent through a solvothermal-high temperature pyrolysis two-step method. The preparation method is green and environment-friendly, does not generate any toxic and harmful byproducts, and has simple preparation process. The composite material can realize the efficient attenuation of microwaves by simply changing the addition amount and the matching thickness of the graphene oxide, when the matching thickness is 1.53mm, the maximum absorption strength reaches-66.0 dB, and when the thickness is 1.56mm, the effective absorption bandwidth reaches 5.2GHz, so that the composite material has important application value in the fields of electromagnetic wave absorption and electromagnetic shielding.
Description
Technical Field
The invention belongs to the technical field of electromagnetic composite materials, and particularly relates to an iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and a preparation method thereof.
Technical Field
With the wide use of electromagnetic equipment in daily life and the rapid development of wireless communication industry, the electromagnetic pollution generated by the electromagnetic radiation has great influence on the environment and human health. In addition, in the military field, the rapid development of modern radio detection technology and radar detection system greatly improves the capability of searching and tracking targets in the war, which makes the traditional war weapons more and more threatened. Microwave absorbing materials (absorbing materials for short) are materials that absorb electromagnetic wave energy projected to the surface of the material and convert the electromagnetic wave energy into heat energy or other forms of energy through the dielectric loss of the material. The ideal wave-absorbing material generally needs to meet the requirements of thin matching thickness, light weight, wide absorption frequency band, high absorption strength and the like. Therefore, the design and development of novel high-performance wave-absorbing materials are increasingly becoming research hotspots in the fields of electronic information and material science.
Graphene has the characteristics of unique two-dimensional lamellar structure, lower density, high specific surface area, excellent conductivity, good chemical stability and the like, so that the graphene attracts much attention in the field of microwave absorption. However, when the graphene is used as a wave-absorbing material, the problems of poor impedance matching property, single attenuation loss mechanism, aggregation of lamella and the like exist. Therefore, there is a need to improve the impedance matching and enhance the attenuation loss performance of graphene.
Metal-Organic Frameworks (MOFs) are a class of crystalline porous materials with a periodic network structure formed by the interconnection of inorganic Metal centers (Metal ions or Metal clusters) and bridged Organic ligands by self-assembly. Due to the structural diversity, porosity, tailorability, ultrahigh specific surface area and other excellent characteristics, the MOFs has wide application prospects in the fields of catalysis, energy storage, separation and the like. Researches find that the magnetic carbon composite material obtained by taking magnetic metal (Fe, Co, Ni and the like) based MOFs as a precursor through a high-temperature pyrolysis strategy has the characteristics of a magnetoelectric synergistic loss mechanism, a multiple heterogeneous interface, a porous structure and the like, and is a potential light wave-absorbing material.
According to the invention, Graphene Oxide (GO) is used as a template, firstly, a FeCoNi trimetal-organic framework (FeCoNi-MOFs) is grown on the surface of the GO in situ by adopting a solvothermal reaction, and then the Fe-CoNi alloy/carbon/graphene composite wave-absorbing material is prepared by high-temperature pyrolysis in an argon atmosphere. The efficient attenuation of the composite material to microwaves can be realized by simply changing the addition amount and the matching thickness of the graphene oxide.
Disclosure of Invention
The invention aims to provide a tri-metal MOFs-derived Fe-Co-Ni alloy/carbon/graphene ultrathin wave-absorbing material and a preparation method thereof.
The invention is realized by the following technical scheme:
a preparation method of a trimetal MOFs derived Fe-Co-Ni alloy/carbon/graphene ultrathin wave-absorbing material is disclosed, wherein the composite material is composed of a porous carbon framework formed by twisting folded graphene into a regular octahedron.
A trimetal MOFs derived iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material is prepared by the following steps:
(1) a150 mL beaker was charged with 60mL of N, N-Dimethylformamide (DMF), 3.6mL of deionized water (H)2O) and 3.6mL ethanol (C)2H5OH), uniformly mixing, adding graphite oxide with certain mass (respectively 0, 16.8mg, 33.6mg, 50.4mg, 67.2mg, 84mg and 100.8mg) while stirring, performing ultrasonic treatment for 1.5h, and stirring for 0.5h to prepare GO dispersion liquid with certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O), 1.0mmol cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 1.0mmol of Nickel nitrate hexahydrate (Ni (NO)3)2·6H2O), stirring vigorously until the mixture is dissolved completely to obtain a mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of trimesic acid (H)3BTC) is stirred vigorously until the mixture is dissolved completely, and then the mixture is stirred for 2 hours;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product.
Compared with the prior art, the beneficial technical effects of the invention are embodied in the following aspects:
1. the three-metal MOFs-derived iron-cobalt-nickel alloy/carbon/graphene composite wave-absorbing material is prepared by adopting a solvothermal-high-temperature pyrolysis two-step method, is simple and convenient to operate, is green and safe, and does not generate any toxic and harmful substances.
2. The iron-cobalt-nickel alloy/carbon/graphene composite wave-absorbing material is composed of a folded graphene entangled regular octahedral carbon framework. The graphitization degree, the magnetic property and the electromagnetic parameter of the composite material can be regulated and controlled by changing the addition amount of the graphene oxide in the precursor, so that the microwave can be efficiently attenuated.
3. The Fe-Co-Ni alloy/carbon/graphene composite material prepared by the invention has excellent wave-absorbing performance, and has the characteristics of low filling ratio, thin matching thickness, high absorption strength, wide absorption frequency band, easy regulation and control of absorption performance and the like. When the thickness is 1.53mm, the maximum absorption intensity can reach-66.0 dB, and when the thickness is 1.56mm, the microwave absorption intensities in the range of 12.8-18.0GHz are all below-10 dB, and the effective absorption bandwidth reaches 5.2 GHz; the effective absorption of electromagnetic waves of different wave bands can be realized by adjusting the addition amount and the matching thickness of the graphene oxide.
4. The Fe-Co-Ni alloy/carbon/graphene composite wave-absorbing material prepared by the invention realizes effective attenuation of electromagnetic waves through the combined action of physical mechanisms such as component cooperation optimization impedance matching, interface polarization, dipole polarization, magnetic loss and the like.
Drawings
FIG. 1 is the XRD spectrum of the product of examples 1, 2, 3, 4, 5, 6, 7;
FIG. 2 is a Raman spectrum of the products of examples 1, 2, 3, 4, 5, 6, 7;
FIG. 3 is an XPS spectrum of the product S5 of example 5;
FIG. 4 is a TEM photograph of product S5 of example 5;
FIG. 5 is a diagram of the hysteresis loop of the product of examples 1, 2, 3, 4, 5, 6, 7 (the upper left corner is a partial enlarged view of the hysteresis loop);
FIG. 6 is a graph of reflection loss versus frequency for product S1 of example 1;
FIG. 7 is a graph of the reflection loss versus frequency for product S2 of example 2;
FIG. 8 is a graph of the reflection loss versus frequency for product S3 of example 3;
FIG. 9 is a graph of the reflection loss versus frequency for product S4 of example 4;
FIG. 10 is a graph of the reflection loss versus frequency for product S5 of example 5;
FIG. 11 is a graph of the reflection loss versus frequency for product S6 of example 6;
FIG. 12 is a graph of the reflection loss versus frequency for product S7 of example 7;
FIG. 13 is a plot of the decay constant versus frequency for the products of examples 1, 2, 3, 4, 5, 6, and 7;
fig. 14 is a plot of impedance matching versus frequency for the products of examples 1, 2, 3, 4, 5, 6, and 7.
Detailed description of the invention
The invention will now be further described with reference to the examples and the accompanying drawings in which:
example 1
(1) 1 150mL beaker was charged with 60mL DMF, 3.6mL H2O and 3.6mL C2H5OH, uniformly mixing;
(2) to the GO dispersion obtained above was added 1.0mmol Fe (NO)3)3·9H2O、1.0mmol Co(NO3)2·6H2O and 1.0mmol Ni (NO)3)2·6H2O, stirring vigorously toCompletely dissolving to obtain mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of H3Stirring BTC vigorously until the BTC is dissolved completely, and then continuing stirring for 2 h;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product, which is recorded as S1.
The XRD spectrum of the product of example 1 is shown in figure 1, and 2 theta is 43.9 degrees, 51.3 degrees and 75.5 degrees, which are consistent with the positions corresponding to the crystal planes of (111), (200) and (220) of a standard card of iron-nickel alloy (JCPDS No. 047-. The raman spectrum of the product of example 1 is shown in fig. 2; s1 at 1594cm-1(G band) 1347cm-1Two distinct diffraction peaks, I, near the (D band)D/IGIs 1.03. The hysteresis loop of the product of example 1 is shown in FIG. 5, and from a partial enlargement of the low-field hysteresis loop, the saturation magnetization is 123.3 emu/g. The powder product of example 1 and paraffin were mixed in a mass ratio of 3: 7, pressing the sample 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 the electromagnetic parameters of the sample by using an AV3629D vector network analyzer, and calculating to obtain the wave-absorbing performance, wherein the testing frequency range is 2-18 GHz. The reflection loss versus frequency curve of sample S1 is shown in FIG. 6, and the maximum absorption intensity reached-7.8 dB at 9.68GHz with a matching thickness of 3.0 mm. The decay constant versus frequency curve for the product of example 1 is shown in FIG. 13; shows a rising trend in the entire frequency range, the maximum of whichIt was 97.86. The impedance matching versus frequency curve of the product of example 1 is shown in fig. 14; its | Zin/Z0The closer the value of | is to 1, indicating better impedance matching, S1 impedance matching deviates far from 1 and therefore has poor impedance matching.
Example 2
(1) 1 150mL beaker was charged with 60mL DMF, 3.6mL H2O and 3.6mL C2H5OH, uniformly mixing, adding 16.8mg of graphite oxide while stirring, performing ultrasonic treatment for 1.5 hours, and stirring for 0.5 hour to prepare a GO dispersion liquid with a certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol Fe (NO)3)3·9H2O、1.0mmol Co(NO3)2·6H2O and 1.0mmol Ni (NO)3)2·6H2O, violently stirring until the O is completely dissolved to obtain a mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of H3Stirring BTC vigorously until the BTC is dissolved completely, and then continuing stirring for 2 h;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product, which is recorded as S2.
The XRD spectrum of the product of example 2 is shown in figure 1, and 2 theta is 43.9 degrees, 51.3 degrees and 75.5 degrees, which are consistent with the positions corresponding to the crystal planes of (111), (200) and (220) of the standard card of iron-nickel alloy (JCPDS No. 047-. The raman spectrum of the product of example 2 is shown in fig. 2;s2 at 1594cm-1(G band) 1347cm-1Two distinct diffraction peaks, I, near the (D band)D/IGIs 1.02. The hysteresis loop diagram of the product of example 2 is shown in fig. 5, and the saturation magnetization is 118.6emu/g as can be seen from the partial enlarged view of the low-field hysteresis loop, and the introduction of graphene is found to reduce the saturation magnetization of the composite material. The powder product of example 2 and paraffin were mixed in a mass ratio of 3: 7, pressing the sample 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 the electromagnetic parameters of the sample by using an AV3629D vector network analyzer, and calculating to obtain the wave-absorbing performance, wherein the testing frequency range is 2-18 GHz. The reflection loss versus frequency curve of sample S2 is shown in FIG. 7, where the maximum absorption strength reached-8.2 dB at 8.72GHz with a matching thickness of 3.5 mm. The decay constant versus frequency curve for the product of example 2 is shown in FIG. 13; a rising trend was exhibited over the entire frequency range with a maximum value of 74.46. The impedance matching versus frequency curve of the product of example 2 is shown in fig. 14; its | Zin/Z0The closer the value of | is to 1, indicating better impedance matching, S2 impedance matching deviates far from 1 and therefore has poor impedance matching.
Example 3
(1) 1 150mL beaker was charged with 60mL DMF, 3.6mL H2O and 3.6mL C2H5OH, uniformly mixing, adding 33.6mg of graphite oxide while stirring, performing ultrasonic treatment for 1.5 hours, and stirring for 0.5 hour to prepare a GO dispersion liquid with a certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol Fe (NO)3)3·9H2O、1.0mmol Co(NO3)2·6H2O and 1.0mmol Ni (NO)3)2·6H2O, violently stirring until the O is completely dissolved to obtain a mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of H3Stirring BTC vigorously until the BTC is dissolved completely, and then continuing stirring for 2 h;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product, which is recorded as S3.
The XRD spectrum of the product of example 3 is shown in figure 1, and 2 theta is 43.9 degrees, 51.3 degrees and 75.5 degrees, which are consistent with the positions corresponding to the crystal planes of (111), (200) and (220) of the standard card of iron-nickel alloy (JCPDS No. 047-. The raman spectrum of the product of example 3 is shown in fig. 2; s3 at 1594cm-1(G band) 1347cm-1Two distinct diffraction peaks, I, near the (D band)D/IGIs 1.01. The hysteresis loop diagram of the product of example 3 is shown in fig. 5, and as can be seen from the partial enlarged view of the low-field hysteresis loop, the saturation magnetization is 108.7emu/g, and the introduction of graphene is found to reduce the saturation magnetization of the composite material. The powder product of example 3 and paraffin were mixed in a mass ratio of 3: 7, pressing the sample 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 the electromagnetic parameters of the sample by using an AV3629D vector network analyzer, and calculating to obtain the wave-absorbing performance, wherein the testing frequency range is 2-18 GHz. The reflection loss versus frequency curve of sample S3 is shown in FIG. 8, where the maximum absorption strength reached-16.98 dB at 8.0GHz with a matching thickness of 3.5 mm. The decay constant versus frequency curve for the product of example 2 is shown in FIG. 13; a rising trend was exhibited over the entire frequency range with a maximum value of 154.55. The impedance matching versus frequency curve of the product of example 3 is shown in fig. 14; its | Zin/Z0The closer the value of | is to 1, indicating better impedance matching, S3 impedance matching deviates far from 1 and therefore has poor impedance matching.
Example 4
(1) Taking 1 150mL beaker, adding60mL of DMF, 3.6mL of H2O and 3.6mL C2H5OH, uniformly mixing, adding 50.4mg of graphite oxide while stirring, performing ultrasonic treatment for 1.5 hours, and stirring for 0.5 hour to prepare a GO dispersion liquid with a certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol Fe (NO)3)3·9H2O、1.0mmol Co(NO3)2·6H2O and 1.0mmol Ni (NO)3)2·6H2O, violently stirring until the O is completely dissolved to obtain a mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of H3Stirring BTC vigorously until the BTC is dissolved completely, and then continuing stirring for 2 h;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product, which is recorded as S4.
The XRD spectrum of the product of example 4 is shown in figure 1, and 2 theta is 43.9 degrees, 51.3 degrees and 75.5 degrees, which are consistent with the positions corresponding to the crystal planes of (111), (200) and (220) of the standard card of iron-nickel alloy (JCPDS No. 047-. The raman spectrum of the product of example 4 is shown in fig. 2; s4 at 1594cm-1(G band) 1347cm-1Two distinct diffraction peaks, I, near the (D band)D/IGIs 1.00. The hysteresis loop diagram of the product of example 4 is shown in fig. 5, and as can be seen from the partial enlarged view of the low-field hysteresis loop, the saturation magnetization is 107.1emu/g, and the introduction of graphene is found to reduce the saturation magnetization of the composite material. Will be provided withThe powder product of example 4 and paraffin wax were mixed in a mass ratio of 3: 7, pressing the sample 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 the electromagnetic parameters of the sample by using an AV3629D vector network analyzer, and calculating to obtain the wave-absorbing performance, wherein the testing frequency range is 2-18 GHz. The curve of the reflection loss with frequency of the sample S4 is shown in FIG. 9, and when the matching thickness is 4.0mm, the maximum absorption intensity reaches-31.6 dB at 6.8GHz, and when the matching thickness is 2.5mm, the microwave absorption intensity is below-10 dB at 9.8-14.8GHz, and the sample has a maximum absorption bandwidth of 5.0 GHz. The decay constant versus frequency curve for the product of example 4 is shown in FIG. 13; a rising trend was exhibited over the entire frequency range with a maximum value of 172.76. The impedance matching versus frequency curve of the product of example 4 is shown in FIG. 14; its | Zin/Z0The closer the value of | is to 1, indicating better impedance matching, S4 impedance matching deviates far from 1 and therefore has poor impedance matching.
Example 5
(1) 1 150mL beaker was charged with 60mL DMF, 3.6mL H2O and 3.6mL C2H5OH, uniformly mixing, adding 67.2mg of graphite oxide while stirring, performing ultrasonic treatment for 1.5 hours, and stirring for 0.5 hour to prepare a GO dispersion liquid with a certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol Fe (NO)3)3·9H2O、1.0mmol Co(NO3)2·6H2O and 1.0mmol Ni (NO)3)2·6H2O, violently stirring until the O is completely dissolved to obtain a mixed dispersion liquid;
(3) adding 1.5mmol of H3BTC into the obtained mixed dispersion liquid, stirring vigorously until the H3BTC is dissolved completely, and continuing stirring for 2H;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product, which is recorded as S5.
The XRD spectrum of the product of example 5 is shown in figure 1, and 2 theta is 43.9 degrees, 51.3 degrees and 75.5 degrees, which are consistent with the positions corresponding to the crystal planes of (111), (200) and (220) of the standard card of iron-nickel alloy (JCPDS No. 047-. The raman spectrum of the product of example 5 is shown in fig. 2; s5 at 1594cm-1(G band) 1347cm-1Two distinct diffraction peaks, I, near the (D band)D/IGIs 0.95. The XPS spectrum of the product of example 5 is shown in FIG. 3, and it can be seen that the sample contains Fe, Co, Ni, C and O elements, which are consistent with the element types in the prepared composite material. Fig. 4 is a TEM photograph of example 5, which shows that the morphology of the carbon framework exhibits a uniform octahedral morphology, and that the carbon framework is attached to the wrinkled graphene sheets. The hysteresis loop diagram of the product of example 5 is shown in fig. 5, and as can be seen from a partial enlarged view of the low-field hysteresis loop, the saturation magnetization is 101.2emu/g, and the introduction of graphene is found to reduce the saturation magnetization of the composite material. The powder product of example 5 and paraffin were mixed in a mass ratio of 3: 7, pressing the sample 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 the electromagnetic parameters of the sample by using an AV3629D vector network analyzer, and calculating to obtain the wave-absorbing performance, wherein the testing frequency range is 2-18 GHz. The curve of the reflection loss with frequency of the sample S5 is shown in FIG. 10, and when the matching thickness is 1.53mm, the maximum absorption intensity reaches-66.0 dB at 15.6GHz, and when the matching thickness is 1.56mm, the microwave absorption intensity is below-10 dB at 12.8-18.0GHz, the sample has a maximum absorption bandwidth of 5.2 GHz. The decay constant versus frequency curve for the product of example 5 is shown in FIG. 13; a rising trend was exhibited over the entire frequency range with a maximum value of 258.24. The impedance matching versus frequency curve of the product of example 5 is shown in FIG. 14; its | Zin/Z0The closer the value of | is to 1, the better the impedance match is, and S5 has the impedance match closest to 1, and thus the optimal impedance match.
Example 6
(1) 1 150mL beaker was charged with 60mL DMF, 3.6mL H2O and 3.6mL C2H5OH, uniformly mixing, adding 84mg of graphite oxide while stirring, performing ultrasonic treatment for 1.5 hours, and stirring for 0.5 hour to prepare a GO dispersion liquid with a certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol Fe (NO)3)3·9H2O、1.0mmol Co(NO3)2·6H2O and 1.0mmol Ni (NO)3)2·6H2O, violently stirring until the O is completely dissolved to obtain a mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of H3Stirring BTC vigorously until the BTC is dissolved completely, and then continuing stirring for 2 h;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product, which is recorded as S6.
The XRD spectrum of the product of example 6 is shown in figure 1, and 2 theta is 43.9 degrees, 51.3 degrees and 75.5 degrees, which are consistent with the positions corresponding to the crystal planes of (111), (200) and (220) of the standard card of iron-nickel alloy (JCPDS No. 047-. The raman spectrum of the product of example 6 is shown in fig. 2; s6 at 1594cm-1(G band) 1347cm-1Two distinct diffraction peaks, I, near the (D band)D/IGIs 0.92. The hysteresis loop diagram of the product of example 6 is shown in fig. 5, and the saturation magnetization is 90.8emu/g as can be seen from the partial enlarged view of the low-field hysteresis loop, and the introduction of graphene is found to reduce the saturation magnetization of the composite material. The powder product of example 6 and paraffin were mixed in a mass ratio of 3: 7, pressing the sample 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 the electromagnetic parameters of the sample by using an AV3629D vector network analyzer, and calculating to obtain the wave-absorbing performance, wherein the testing frequency range is 2-18 GHz. The curve of the reflection loss with frequency of the sample S6 is shown in FIG. 11, when the matching thickness is 1.56mm, the maximum absorption intensity reaches-50.5 dB at 14.64GHz, the microwave absorption intensities are all below-10 dB at 12.8-18.0GHz under the same matching thickness, and the sample has a maximum absorption bandwidth of 5.2 GHz. The decay constant versus frequency curve for the product of example 6 is shown in FIG. 13; a rising trend was exhibited over the entire frequency range with a maximum value of 250.2. The impedance matching versus frequency curve of the product of example 6 is shown in FIG. 14; its | Zin/Z0The closer the value of | is to 1, the better the impedance match is, and S6 has an impedance match around 1, and thus has a better impedance match.
Example 7
(1) 1 150mL beaker was charged with 60mL DMF, 3.6mL H2O and 3.6m C2H5OH, uniformly mixing, adding 100.8mg of graphite oxide while stirring, performing ultrasonic treatment for 1.5 hours, and stirring for 0.5 hour to prepare a GO dispersion liquid with a certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol Fe (NO)3)3·9H2O、1.0mmol Co(NO3)2·6H2O and 1.0mmol Ni (NO)3)2·6H2O, violently stirring until the O is completely dissolved to obtain a mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of H3Stirring BTC vigorously until the BTC is dissolved completely, and then continuing stirring for 2 h;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and carrying out vacuum drying for 24h at 55 ℃ to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product, which is recorded as S7.
The XRD spectrum of the product of example 7 is shown in figure 1, and 2 theta is 43.9 degrees, 51.3 degrees and 75.5 degrees, which are consistent with the positions corresponding to the crystal planes of (111), (200) and (220) of the standard card of iron-nickel alloy (JCPDS No. 047-. The raman spectrum of the product of example 7 is shown in fig. 2; s7 at 1594cm-1(G band) 1347cm-1Two distinct diffraction peaks, I, near the (D band)D/IGIs 0.90. The hysteresis loop diagram of the product of example 7 is shown in fig. 5, and as can be seen from the partial enlarged view of the low-field hysteresis loop, the saturation magnetization is 69.7emu/g, and the introduction of graphene is found to reduce the saturation magnetization of the composite material. The powder product of example 7 and paraffin were mixed in a mass ratio of 3: 7, pressing the sample 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 the electromagnetic parameters of the sample by using an AV3629D vector network analyzer, and calculating to obtain the wave-absorbing performance, wherein the testing frequency range is 2-18 GHz. The curve of the reflection loss with frequency of the sample S7 is shown in FIG. 12, when the matching thickness is 1.5mm, the maximum absorption intensity reaches-25.6 dB at 15.28GHz, the microwave absorption intensities are all below-10 dB at 13.1-18.0GHz under the same matching thickness, and the sample has a maximum absorption bandwidth of 4.9 GHz. The decay constant versus frequency curve for the product of example 7 is shown in FIG. 13; a rising trend was exhibited over the entire frequency range with a maximum value of 264.83. The impedance matching versus frequency curve for the product of example 7 is shown in FIG. 14; its | Zin/Z0The closer the value of | is to 1, indicating better impedance match, S7 impedanceThe matching is around 1, so that the impedance matching is better.
According to the test results of the embodiment, the three-metal MOFs-derived iron-cobalt-nickel alloy/carbon/graphene composite wave-absorbing material is obtained through a solvothermal-high-temperature pyrolysis two-step method, and the method is simple to operate, safe, green and free of toxic and harmful substances. The sample S5 has comprehensive and optimal wave-absorbing performance, when the thickness is 1.53mm, the maximum absorption strength can reach-66.0 dB, and when the thickness is 1.56mm, the effective absorption bandwidth can reach 5.2 GHz; the electromagnetic waves of different wave bands can be effectively absorbed by adjusting the addition amount and the matching thickness of the graphene oxide. Therefore, the prepared Fe-Co-Ni alloy/carbon/graphene composite material is an ideal light ultrathin wave-absorbing material.
Claims (9)
1. A preparation method of a trimetal-organic framework (FeCoNi-MOFs) derived Fe-Co-Ni alloy/carbon/graphene ultrathin wave-absorbing material is characterized by comprising the following steps: the composite material consists of a porous carbon framework of pleated graphene entangled regular octahedra.
The composite wave-absorbing material is prepared by the following steps:
(1) a150 mL beaker was charged with 60mL of N, N-Dimethylformamide (DMF), 3.6mL of deionized water (H)2O) and 3.6mL ethanol (C)2H5OH), uniformly mixing, adding graphite oxide with certain mass (respectively 0 mg, 16.8mg, 33.6mg, 50.4mg, 67.2mg, 84mg and 100.8mg) while stirring, performing ultrasonic treatment for 1.5h, and stirring for 0.5h to prepare a Graphene Oxide (GO) dispersion liquid with certain concentration;
(2) to the GO dispersion obtained above was added 1.0mmol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O), 1.0mmol cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 1.0mmol of Nickel nitrate hexahydrate (Ni (NO)3)2·6H2O), stirring vigorously until the mixture is dissolved completely to obtain a mixed dispersion liquid;
(3) to the mixed dispersion obtained above was added 1.5mmol of trimesic acid (H)3BTC) is stirred vigorously until the mixture is dissolved completely, and then the mixture is stirred for 2 hours;
(4) transferring the mixed dispersion liquid into a polytetrafluoroethylene-lined autoclave with the volume of 100mL, and carrying out solvothermal reaction for 24h at the temperature of 150 ℃;
(5) after the reaction is finished, cooling to room temperature, repeatedly carrying out centrifugal washing for multiple times by using DMF and absolute ethyl alcohol, and collecting precipitates;
(6) transferring the collected precipitate to a vacuum drying oven, and vacuum-drying at 55 ℃ for 24h to constant weight to obtain a precursor;
(7) and (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace in an argon atmosphere, wherein the temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and cooling to room temperature to obtain a final product.
2. The method of preparing the trimetal MOFs-derived Fe-Co-Ni alloy/carbon/graphene composite material according to claim 1, wherein the method comprises the following steps: the mixed solvents DMF and H in the step (1)2O and C2H5The volume ratio of OH is 50:3: 3.
3. The method of preparing the trimetal MOFs-derived Fe-Co-Ni alloy/carbon/graphene composite material according to claim 1, wherein the method comprises the following steps: fe (NO) in the step (2)3)3·9H2O、Co(NO3)2·6H2O and Ni (NO)3)2·6H2The molar ratio of O is 1:1: 1.
4. The method of preparing the trimetal MOFs-derived Fe-Co-Ni alloy/carbon/graphene composite material according to claim 1, wherein the method comprises the following steps: the step (3) must be performed by adding H first3After the BTC was stirred vigorously to dissolve completely, stirring was continued for 2 h.
5. The method of preparing the trimetal MOFs-derived Fe-Co-Ni alloy/carbon/graphene composite material according to claim 1, wherein the method comprises the following steps: the solvothermal reaction condition of the step (4) must be 150 ℃ for 24 hours.
6. The method of preparing the trimetal MOFs-derived Fe-Co-Ni alloy/carbon/graphene composite material according to claim 1, wherein the method comprises the following steps: after the reaction in the step (5) is finished, the precipitate is obtained by firstly carrying out centrifugal washing on DMF for 5 times and then carrying out centrifugal washing on absolute ethyl alcohol for 3 times.
7. The method of preparing the trimetal MOFs-derived Fe-Co-Ni alloy/carbon/graphene composite material according to claim 1, wherein the method comprises the following steps: in the step (6), the precursor must be obtained by vacuum drying.
8. The trimetallic MOFs-derived iron-cobalt-nickel alloy/carbon/graphene composite material according to claim 1, wherein: in the step (7), the high-temperature pyrolysis process of the precursor is carried out in the argon protective atmosphere, the heating rate is 5 ℃/min, the temperature is controlled at 700 ℃, and the temperature is kept for 2 h.
9. A trimetal MOFs-derived Fe-Co-Ni alloy/carbon/graphene composite wave-absorbing material prepared by the preparation method of any one of claims 1 to 8.
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