CN112961650B - Three-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof - Google Patents
Three-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-Metal Organic Frameworks (MOFs) derived iron-nickel alloy/porous carbon ultrathin wave absorber and a preparation method thereof. Iron salt, zinc salt and nickel salt of different kinds are used as precursors, trimesic acid is used as an organic ligand, N, N-dimethylformamide, deionized water and absolute ethyl alcohol are used as mixed solvents, polyvinylpyrrolidone is used as a stabilizer, and the iron-zinc-nickel trimetallic MOFs derivative iron-nickel alloy/porous carbon composite wave-absorbing material is prepared through a solvothermal and pyrolysis two-step method. 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 gradually evolve from a porous shape to a pomegranate shape, a hollow structure and a core-shell structure by simply changing the salt type in the precursor, and meanwhile, the calcination temperature and the matching thickness are changed to realize strong absorption and wide bandwidth, so that the Ku wave band is almost completely covered by effective absorption, and 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 field of electromagnetic wave absorbing materials, and particularly relates to a preparation method of a three-metal organic framework derived iron-nickel alloy/porous carbon composite wave absorbing material.
Technical Field
With the development of radio technology and information industry, electronic products are widely applied, and a series of electromagnetic radiation problems are brought along with the development of the radio technology and the information industry, so that the production and the life of people are affected. 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 search for effective techniques to reduce or eliminate electromagnetic radiation is of great importance in the life and military fields. An important way of reducing electromagnetic radiation is electromagnetic wave absorption. Earlier studies show that the wave absorbing material can promote electromagnetic energy to be converted into heat energy or eliminate electromagnetic wave radically through interference cancellation, thereby achieving the purpose of eliminating electromagnetic radiation. In practical application, the novel electromagnetic wave absorbing material meeting the requirements of thin thickness, light weight, wide absorption frequency band and high absorption intensity has important application prospect.
The porous carbon is used as a novel wave-absorbing material, so that the coating difficulty is reduced, the wave-absorbing effect is enhanced, and the urgent requirements of 'thin, light, wide and strong' of the stealth material of the aircraft are easily met. Compared with a nonporous material, the porous carbon material is light, and along with the continuous deepening of people, the large specific surface area and the pore structure of the porous carbon material are found to be favorable for absorbing incident electromagnetic waves, so that the electromagnetic waves are converted into heat energy to be consumed, and the attenuation of the electromagnetic waves is achieved.
Metal-organic frameworks (Metal-Organic Frameworks, MOFs) are a novel class of pore-size crystalline materials that form three-dimensional structures from the complexation of adjustable Metal ions with organic ligands. The biggest advantage of MOFs materials over traditional pore materials (molecular sieves, activated carbon, etc.) is their variable and tunable metal ion and ligand composition. MOFs have the advantages of three-dimensional pore structure, high porosity, low density, large specific surface area, regular pore canal, adjustable pore diameter, topological structure diversity, tailorability and the like, and due to the highly ordered pore structure and a large amount of organic ligand components, the MOFs material can be used as a precursor or a template to obtain a porous carbon material through high-temperature heat treatment.
The magnetic metal has the characteristics of larger saturation magnetization intensity, higher Snoek limit, compatible dielectric-magnetic loss and the like, and has wide application in the field of electromagnetic wave absorption. The alloy has the characteristics of double components, and compared with single-component magnetic metal, the magnetic metal alloy has the characteristics of stronger electron transfer and spin polarization coupling, and has certain advantages in the field of electromagnetic wave absorption. In addition, the magnetic alloy and carbon are compounded to slow down the oxidation of the alloy and reduce the density. The magnetic alloy/carbon composite material has double loss characteristics of magnetic loss and dielectric loss, and has wide application in the field of electromagnetic wave absorption.
According to the invention, a solvothermal reaction is adopted to synthesize FeZnNi trimetallic MOFs, and then the iron-nickel alloy/porous carbon composite wave-absorbing material is prepared by pyrolysis in an argon atmosphere. The morphology of the carbon framework gradually evolves from a porous state to a pomegranate-like, hollow structure and core-shell structure by simply changing the salt type in the precursor; the effective absorption of the composite material to electromagnetic waves of different wave bands can be realized by adjusting the salt types, the calcination temperature and the matching thickness in the precursor.
Disclosure of Invention
The invention aims to provide a three-metal organic frame derived iron-nickel alloy/porous carbon composite wave-absorbing material and a preparation method thereof, and the composite material has the characteristics of thin thickness, high absorption strength, wide absorption frequency band, 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 three-metal organic framework derived iron-nickel alloy/porous carbon composite wave-absorbing material is composed of iron-nickel alloy and porous carbon.
A three-metal organic framework derived iron-nickel alloy/porous carbon composite wave-absorbing material comprises the following preparation steps:
(1) 1 of a 150mL beaker was taken and 60mL of N, N-Dimethylformamide (DMF), 3.6mL of deionized water (H) 2 O) and 3.6mL of absolute ethanol (C) 2 H 5 OH), and 1.0mmol of iron salt, 1.0mmol of zinc salt and 1.0mmol of nickel salt are weighed, and are added in turn, vigorously stirred until being completely dissolved, to obtain mixed solutions (iron salt, zinc salt and nickel salt are respectively: ferric chloride hexahydrate (FeCl) 3 ·6H 2 O), zinc chloride (ZnCl) 2 ) And nickel chloride hexahydrate (NiCl) 2 ·6H 2 O); ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O), zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O)；FeCl 3 ·6H 2 O、ZnCl 2 And Ni (NO) 3 ) 2 ·6H 2 O; ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O)、Zn(NO 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O)；
(2) To the above solution was added 1.5mmol of trimesic acid (H 3 BTC) is vigorously stirred until the mixture is completely dissolved, 1.0g of polyvinylpyrrolidone (PVP, K-30) is added, and the mixture is vigorously stirred until the mixture is completely dissolved, and finally, the mixture is vigorously stirred for 2 hours to obtain a uniform solution;
(3) Transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
(4) 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tubular furnace in an argon atmosphere, wherein the temperatures are 700, 800, 900 and 950 ℃, 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 two steps of solvothermal and high-temperature pyrolysis to prepare the trimetallic MOFs derived iron-nickel alloy/porous carbon composite wave-absorbing material, which is simple and convenient to operate, green and safe and has no toxic and harmful substances.
2. The invention combines different salt types of three metal salts, and discovers that the morphology of a carbon framework gradually evolves from a porous state to a pomegranate-like, hollow structure and core-shell structure by simply changing the salt types in a precursor.
3. The invention discovers that the salt type has great influence on the wave absorbing performance of the composite material. Studies have shown that when the three metal salts are FeCl respectively 3 ·6H 2 O、ZnCl 2 、NiCl 2 ·6H 2 And in the process of O, the composite material simultaneously has the characteristics of thin thickness, strong absorption, wide frequency band and the like.
4. The invention discovers that the calcining temperature has great influence on the morphology and the wave absorbing performance of the composite material, and when the calcining temperature is 900 ℃, the morphology of the carbon framework is porous, and the wave absorbing performance is optimal.
5. The iron-nickel alloy/porous carbon composite wave-absorbing material prepared by the invention has excellent wave-absorbing performance, and the maximum absorption strength can reach-66.4 dB at the thickness of 1.35 mm; the microwave absorption intensity is below-10 dB in the range of 12.3-18.0GHz under the thickness of 1.4mm, the effective absorption bandwidth reaches 5.7GHz, 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 the composite material by adjusting the salt types, the calcination temperature and the matching thickness in the precursor.
6. The iron-nickel alloy/porous 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 loss and the like.
Drawings
FIG. 1 is XRD patterns of the products of examples 1,2, 3 and 4;
FIG. 2 is XRD patterns of the products of examples 5, 6 and 7;
FIG. 3 is a graph of TG curves of the product precursors of examples 1,2, 3, and 4;
FIG. 4 is a Raman spectrum of the product of examples 1,2, 3, 4;
FIG. 5 is a Raman spectrum of the product of examples 5, 6, 7;
FIG. 6 is an XPS spectrum of product S3 in example 3;
FIG. 7 is an SEM photograph of the products of examples 1,2, 3 and 4;
FIG. 8 is an SEM photograph of the products of examples 5, 6 and 7;
FIG. 9 is a plot of reflection loss of product S1 as a function of frequency in example 1;
FIG. 10 is a plot of reflection loss of product S2 as a function of frequency for example 2;
FIG. 11 is a plot of reflection loss of product S3 as a function of frequency in example 3;
FIG. 12 is a plot of reflection loss of product S4 as a function of frequency for example 4;
FIG. 13 is a graph showing the reflection loss of the product S5 in example 5 as a function of frequency;
FIG. 14 is a plot of reflection loss of product S6 as a function of frequency for example 6;
fig. 15 is a graph showing the reflection loss of the product S7 in example 7 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. 1 beaker of 150mL was taken and 60mL DMF,3.6mL H was added 2 O and 3.6mL C 2 H 5 OH, mixing well, weighing 1.0mmol FeCl 3 ·6H 2 O，1.0mmol ZnCl 2 And 1.0mmol NiCl 2 ·6H 2 Adding O in sequence, and stirring vigorously until the O is completely dissolved to obtain a uniform solution;
2. to the homogeneous solution obtained above, 1.5mmol of H was added 3 After the BTC is vigorously stirred to be completely dissolved, 1.0g of PVP is added, and after the BTC is vigorously stirred to be completely dissolved, the BTC is finally vigorously stirred for 2 hours;
3. transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
4. 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tubular furnace filled with argon, wherein the temperature is 700 ℃, 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 were shown in fig. 1,2θ=31.7°,34.4°,36.2 °,47.6 °,56.6 °, and 62.8 ° corresponding to the positions corresponding to the (100), (002), (101), (102), (110) and (103) crystal planes of the zinc oxide (ZnO) standard Card (JCPDS Card No. 89-0510). 2θ=43.7°,50.8 ° and 74.7 ° are consistent with positions corresponding to (111), (200) and (220) crystal planes of an iron-nickel (FeNi) alloy standard Card (JCPDS Card No. 47-1417). 2θ=42.7, 49.7° and 73.2 ° coincide with positions corresponding to (111), (200) and (220) crystal planes of an iron (Fe) standard Card (JCPDS Card No. 52-0513). The TG curve of the precursor of the product of example 1 is shown in fig. 3; under nitrogen atmosphere, the temperature rising rate is 10 ℃/min at 30-900 ℃. The weight loss of FeZnNi-MOFs pyrolysis is between 30 and 245 ℃, between 245 and 532 ℃ respectively, of 17.5 and 54.3wt.%. The first stage is mainly evaporation of adsorbed water, and the second stage is mainly decomposition of organic ligands. The raman spectrum of the product of example 1 is shown in fig. 4; s1 at 1602cm -1 (G band) 1336cm -1 There are two distinct diffraction peaks near (band D), I D /I G 0.92. SEM photographs of the product of example 1 are shown in fig. 7 (a); at 700 deg.C, is expressed as surface roughnessFlat microspheres. The powder product and paraffin wax in the example 1 are pressed into coaxial samples with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special mould according to the mass ratio of 5:5, electromagnetic parameters are tested by using an AV3629D vector network analyzer, the wave absorption performance is obtained through calculation, and the testing frequency range is 2.0-18.0GHz. The reflection loss versus frequency curve of sample S1 is shown in FIG. 9, and the maximum absorption strength reaches-12.8 dB at 7.6GHz when the matching thickness is 3.5 mm.
Example 2
1. 1 beaker of 150mL was taken and 60mL DMF,3.6mL H was added 2 O and 3.6mL C 2 H 5 OH, mixing well, weighing 1.0mmol FeCl 3 ·6H 2 O，1.0mmol ZnCl 2 And 1.0mmol NiCl 2 ·6H 2 Adding O in sequence, and stirring vigorously until the O is completely dissolved to obtain a uniform solution;
2. to the homogeneous solution obtained above, 1.5mmol of H was added 3 After the BTC is vigorously stirred to be completely dissolved, 1.0g of PVP is added, and after the BTC is vigorously stirred to be completely dissolved, the BTC is finally vigorously stirred for 2 hours;
3. transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
4. 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tube furnace filled with argon, wherein the temperature is 800 ℃, 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.
The XRD patterns of the product of example 2 are shown in fig. 1,2θ=43.7°,50.8 ° and 74.7 ° corresponding to the (111), (200) and (220) crystal planes of the FeNi alloy standard Card (JCPDS Card No. 47-1417). The TG curve of the precursor of the product of example 2 is shown in fig. 3; under nitrogen atmosphere, the temperature rising rate is 10 ℃/min at 30-900 ℃. Weight of FeZnNi-MOFs pyrolysisLosses are 17.5wt.% and 54.3wt.% at 30-245 ℃, 245-532 ℃, respectively. The first stage is mainly evaporation of adsorbed water, and the second stage is mainly decomposition of organic ligands. The raman spectrum of the product of example 2 is shown in fig. 4; s2 at 1602cm -1 (G band) 1336cm -1 There are two distinct diffraction peaks near (band D), I D /I G 0.87. SEM photographs of the product of example 2 are shown in fig. 7 (b); the microspheres show smooth surface at 800 ℃. The powder product and paraffin wax in the example 2 are pressed into coaxial samples with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special mould according to the mass ratio of 5:5, electromagnetic parameters are tested by using an AV3629D vector network analyzer, the wave absorption performance is obtained through calculation, and the testing frequency range is 2.0-18.0GHz. The reflection loss versus frequency curve of sample S2 is shown in FIG. 10, and the maximum absorption strength reaches-62.4 dB at 17.4GHz when the matching thickness is 1.53 mm. When the matching thickness is 1.78mm, the microwave absorption intensity is below-10 dB in the range of 12.6-18.0GHz, and the effective absorption bandwidth reaches 5.4GHz.
Example 3
1. 1 beaker of 150mL was taken and 60mL DMF,3.6mL H was added 2 O and 3.6mL C 2 H 5 OH, mixing well, weighing 1.0mmol FeCl 3 ·6H 2 O，1.0mmol ZnCl 2 And 1.0mmol NiCl 2 ·6H 2 Adding O in sequence, and stirring vigorously until the O is completely dissolved to obtain a uniform solution;
2. to the homogeneous solution obtained above, 1.5mmol of H was added 3 After the BTC is vigorously stirred to be completely dissolved, 1.0g of PVP is added, and after the BTC is vigorously stirred to be completely dissolved, the BTC is finally vigorously stirred for 2 hours;
3. transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
4. 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tubular furnace filled with argon, wherein the temperature is 900 ℃, 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.
The XRD patterns of the product of example 3 are shown in fig. 1,2θ=43.7°,50.8 ° and 74.7 ° corresponding to the (111), (200) and (220) crystal planes of the FeNi alloy standard Card (JCPDS Card No. 47-1417). The TG curve of the precursor of the product of example 3 is shown in fig. 3; under nitrogen atmosphere, the temperature rising rate is 10 ℃/min at 30-900 ℃. The weight loss of FeZnNi-MOFs pyrolysis is between 30 and 245 ℃, between 245 and 532 ℃ respectively, of 17.5 and 54.3wt.%. The first stage is mainly evaporation of adsorbed water, and the second stage is mainly decomposition of organic ligands. The raman spectrum of the product of example 3 is shown in fig. 4; s3 at 1602cm -1 (G band) 1336cm -1 There are two distinct diffraction peaks near (band D), I D /I G A calcination temperature of 0.83 indicates an increase in the degree of graphitization. The XPS spectrum of the product of example 3 is shown in FIG. 6, and it can be seen that the sample contains Fe, zn, ni, C and O elements, which are consistent with the types of elements in the prepared composite material. The presence of Zn element indicates the presence of zinc species at 900 ℃ and no diffraction peaks of zinc species were observed in the XRD characterization, indicating that zinc may be evaporated or present in the sample in an amorphous state. SEM photographs of the product of example 3 are shown in fig. 7 (c); the microspheres show holes on the surface at 900 ℃. The powder product and paraffin wax in the embodiment 3 are pressed into coaxial samples with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die according to the mass ratio of 5:5, electromagnetic parameters are tested by using an AV3629D vector network analyzer, the wave absorption performance is obtained through calculation, and the testing frequency range is 2.0-18.0GHz. The reflection loss versus frequency curve of sample S3 is shown in FIG. 11, and the maximum absorption strength reaches-66.4 dB at 15.76GHz when the matching thickness is 1.35 mm. When the matching thickness is 1.4mm, the microwave absorption intensity is below-10 dB in the range of 12.3-18.0GHz, and the effective absorption bandwidth reaches 5.7GHz.
Example 4
1. 1 beaker of 150mL was taken and 60mL DMF,3.6mL H was added 2 O and 3.6mL C 2 H 5 OH, mixing well, weighing 1.0mmol FeCl 3 ·6H 2 O，1.0mmol ZnCl 2 And 1.0mmol NiCl 2 ·6H 2 Adding O in sequence, and stirring vigorously until the O is completely dissolved to obtain a uniform solution;
2. to the homogeneous solution obtained above, 1.5mmol of H was added 3 After the BTC is vigorously stirred to be completely dissolved, 1.0g of PVP is added, and after the BTC is vigorously stirred to be completely dissolved, the BTC is finally vigorously stirred for 2 hours;
3. transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
4. 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tubular furnace filled with argon, wherein the temperature is 950 ℃, 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.
The XRD patterns of the product of example 4 are shown in fig. 1,2θ=43.7°,50.8 ° and 74.7 ° corresponding to the (111), (200) and (220) crystal planes of the FeNi alloy standard Card (JCPDS Card No. 47-1417). The TG curve of the precursor of the product of example 4 is shown in fig. 3; under nitrogen atmosphere, the temperature rising rate is 10 ℃/min at 30-900 ℃. The weight loss of FeZnNi-MOFs pyrolysis is between 30 and 245 ℃, between 245 and 532 ℃ respectively, of 17.5 and 54.3wt.%. The first stage is mainly evaporation of adsorbed water, and the second stage is mainly decomposition of organic ligands. The raman spectrum of the product of example 4 is shown in fig. 4; s4 at 1602cm -1 (G band) 1336cm -1 There are two distinct diffraction peaks near (band D), I D /I G At 0.81, an increase in calcination temperature is indicated, with an increase in graphitization. SEM photographs of the product of example 4 are shown in fig. 7 (d); the microspheres, which exhibited porous surfaces at 950 c, exhibited some collapse, indicating that the morphology of the samples changed as the calcination temperature was increased. The powder product of example 4 and paraffin wax were mixed in a mass ratio of 5:5 in a special mouldPressing into coaxial sample with outer diameter of 7.00mm, inner diameter of 3.04mm and thickness of about 2mm, testing electromagnetic parameters by using model AV3629D vector network analyzer, calculating to obtain wave absorbing performance, and testing frequency range of 2.0-18.0GHz. The reflection loss versus frequency curve of sample S4 is shown in FIG. 12, and the maximum absorption strength reaches-11.27 dB at 5.68GHz when the matching thickness is 2.5 mm.
Example 5
1. 1 beaker of 150mL was taken and 60mL DMF,3.6mL H was added 2 O and 3.6mL C 2 H 5 OH, mixing well, weighing 1.0mmol Fe (NO) 3 ) 3 ·9H 2 O，1.0mmol Zn(NO 3 ) 2 ·6H 2 O and 1.0mmol Ni (NO) 3 ) 2 ·6H 2 Adding O in sequence, and stirring vigorously until the O is completely dissolved to obtain a uniform solution;
2. to the homogeneous solution obtained above, 1.5mmol of H was added 3 After the BTC is vigorously stirred to be completely dissolved, 1.0g of PVP is added, and after the BTC is vigorously stirred to be completely dissolved, the BTC is finally vigorously stirred for 2 hours;
3. transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
4. 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tubular furnace filled with argon, wherein the temperature is 900 ℃, 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.
The XRD patterns of the product of example 5 are shown in fig. 2,2θ=43.7°,50.8 ° and 74.7 ° corresponding to the (111), (200) and (220) crystal planes of the FeNi alloy standard Card (JCPDS Card No. 47-1417). 2θ=44.2°,51.5 ° and 76.1 ° with FeNi 3 The positions corresponding to the (111), (200) and (220) crystal faces of the alloy standard Card (JCPDS Card No. 38-0419) are consistent. Pulling the product of example 5The Mannich spectrogram is shown in FIG. 5; s5 at 1594cm -1 (G band) 1326cm -1 There are two distinct diffraction peaks near (band D), I D /I G 0.88. SEM photographs of the product of example 5 are shown in fig. 8 (a); s5 is expressed as a microsphere with a diameter of about 1 μm, indicating that different salt species have a great influence on the morphology of the sample. The powder product and paraffin wax in the example 5 are pressed into coaxial samples with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special mould according to the mass ratio of 5:5, electromagnetic parameters are tested by using an AV3629D vector network analyzer, the wave absorption performance is obtained through calculation, and the testing frequency range is 2.0-18.0GHz. The reflection loss versus frequency curve of sample S5 is shown in FIG. 13, and the maximum absorption strength reaches-9.0 dB at 5.12GHz when the matching thickness is 3.5 mm.
Example 6
1. 1 beaker of 150mL was taken and 60mL DMF,3.6mL H was added 2 O and 3.6mL C 2 H 5 OH, mixing well, weighing 1mmol FeCl 3 ·6H 2 O，1mmol ZnCl 2 And 1mmol Ni (NO) 3 ) 2 ·6H 2 Adding O in sequence, and stirring vigorously until the O is completely dissolved to obtain a uniform solution;
2. to the homogeneous solution obtained above, 1.5mmol of H was added 3 After the BTC is vigorously stirred to be completely dissolved, 1.0g of PVP is added, and after the BTC is vigorously stirred to be completely dissolved, the BTC is finally vigorously stirred for 2 hours;
3. transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
4. 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tubular furnace filled with argon, wherein the temperature is 900 ℃, 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.
XRD patterns of the product of example 6 are shown in the figure2,2θ=43.7°,50.8 ° and 74.7 ° are consistent with positions corresponding to (111), (200) and (220) crystal planes of the FeNi alloy standard Card (JCPDS Card No. 47-1417). The raman spectrum of the product of example 6 is shown in fig. 5; s6 at 1582cm -1 (G band) 1349cm -1 There are two distinct diffraction peaks near (band D), I D /I G 0.83. SEM photographs of the product of example 6 are shown in fig. 8 (b); s6 is expressed as a microsphere with a diameter of about 10 microns, indicating that different salt species have a great effect on both the morphology and size of the sample. The powder product of example 6 and paraffin wax were mixed in a mass ratio of 5:5, 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, and calculating to obtain the wave absorbing performance, wherein the testing frequency range is 2.0-18.0GHz. The reflection loss versus frequency curve of sample S6 is shown in FIG. 14, and the maximum absorption strength reaches-17.68 dB at 7.84GHz when the matching thickness is 3.0 mm.
Example 7
1. 1 beaker of 150mL was taken and 60mL DMF,3.6mL H was added 2 O and 3.6mL C 2 H 5 OH, mixing well, weighing 1mmol FeCl 2 ·4H 2 O，1mmol Zn(NO 3 ) 2 ·6H 2 O，1mmol Ni(NO 3 ) 2 ·6H 2 Adding O in sequence, and stirring vigorously until the O is completely dissolved to obtain a uniform solution;
2. to the homogeneous solution obtained above, 1.5mmol of H was added 3 After the BTC is vigorously stirred to be completely dissolved, 1.0g of PVP is added, and after the BTC is vigorously stirred to be completely dissolved, the BTC is finally vigorously stirred for 2 hours;
3. transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
4. 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;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature thermal annealing treatment on the precursor in a tubular furnace filled with argon, wherein the temperature is 900 ℃, 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 S7.
The XRD pattern of the product of example 7 is shown in FIG. 2.2θ=43.7°,50.8 ° and 74.7 ° coincide with positions corresponding to (111), (200) and (220) crystal planes of the FeNi alloy standard Card (JCPDS Card No. 47-1417). 2θ=44.2°,51.5 ° and 76.1 ° with FeNi 3 The positions corresponding to the (111), (200) and (220) crystal faces of the alloy standard Card (JCPDS Card No. 38-0419) are consistent. The raman spectrum of the product of example 7 is shown in fig. 5; s7 at 1588cm -1 (G band) 1346cm -1 There are two distinct diffraction peaks near (band D), I D /I G 0.89. SEM photographs of the product of example 7 are shown in fig. 8 (c); s7 is expressed as hollow microspheres with a diameter of about 10 mu m, and the surface of the hollow microspheres is provided with broken holes, which shows that different salt types have great influence on the morphology and the size of the sample. The powder product and paraffin wax in the example 7 are pressed into coaxial samples with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of about 2mm in a special die according to the mass ratio of 5:5, electromagnetic parameters are tested by using an AV3629D vector network analyzer, the wave absorption performance is obtained through calculation, and the testing frequency range is 2.0-18.0GHz. The reflection loss versus frequency curve of sample S7 is shown in FIG. 15, and the maximum absorption strength reaches-20.0 dB at 4.64GHz when the matching thickness is 4.5 mm.
As shown by the test results of the embodiment, the three-metal MOFs derived iron-nickel alloy/porous 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 composite material has excellent comprehensive wave-absorbing performance, and when the matching thickness is 1.35mm, the maximum absorption strength of a sample S3 reaches-66.4 dB; the matching thickness is 1.35mm, the maximum effective absorption bandwidth reaches 5.7GHz, and the Ku wave band is almost completely covered. The electromagnetic waves of different wave bands can be effectively absorbed by the composite material by adjusting the salt types, the calcination temperature and the matching thickness in the precursor. Therefore, the iron-nickel alloy/porous carbon material is an ideal ultrathin and efficient electromagnetic wave absorber.
Claims (7)
1. A preparation method of a trimetallic organic framework derived iron-nickel alloy/porous carbon composite wave-absorbing material is characterized by comprising the following steps: the wave absorbing material consists of iron-nickel alloy and porous carbon;
the composite wave-absorbing material is prepared by the following method:
(1) Taking 1 beaker of 150mL, adding 60mL of N, N-dimethylformamide, 3.6mL of deionized water and 3.6mL of absolute ethyl alcohol, uniformly mixing, weighing 1.0mmol of ferric chloride hexahydrate, 1.0mmol of zinc chloride and 1.0mmol of nickel chloride hexahydrate, and sequentially adding intense stirring until the materials are completely dissolved to obtain a mixed solution;
(2) Adding 1.5mmol of trimesic acid into the solution, stirring vigorously to dissolve completely, adding 1.0g of polyvinylpyrrolidone, stirring vigorously to dissolve completely, and stirring vigorously for 2h to obtain uniform solution;
(3) Transferring the obtained solution into an autoclave with a polytetrafluoroethylene liner and a volume of 100mL, and performing solvothermal reaction for 24 hours at 150 ℃;
(4) After the reaction is finished, cooling to room temperature, repeatedly centrifuging and washing with N, N-dimethylformamide and absolute ethyl alcohol for a plurality of times, and collecting a precipitate;
(5) Transferring the collected precipitate to a vacuum freeze dryer, drying for 24 hours to constant weight, and grinding uniformly to obtain a precursor;
(6) And (3) carrying out high-temperature heat treatment on the precursor in a tubular furnace filled with argon, wherein the calcination temperature is 900 ℃, the heating rate is 5 ℃/min, the heat preservation time is 2h, and the final product is obtained after cooling to room temperature.
2. The method for preparing the trimetallic organic framework-derived iron-nickel alloy/porous carbon composite material according to claim 1, wherein the method comprises the following steps: the step (1) is to add 1.0mmol of ferric chloride hexahydrate and stir vigorously to dissolve completely, then add 1.0mmol of zinc chloride and stir vigorously to dissolve completely, and finally add 1.0mmol of nickel chloride hexahydrate and stir vigorously to dissolve completely.
3. The method for preparing the trimetallic organic framework-derived iron-nickel alloy/porous carbon composite material according to claim 1, wherein the method comprises the following steps: in the step (2), 1.5mmol of trimesic acid is added and stirred vigorously until the trimesic acid is completely dissolved, 1.0g of polyvinylpyrrolidone is added and stirred vigorously until the trimesic acid and the polyvinylpyrrolidone are completely dissolved, and the mixture is stirred for 2 hours after the trimesic acid and the polyvinylpyrrolidone are completely dissolved.
4. The method for preparing the trimetallic organic framework-derived iron-nickel alloy/porous carbon composite material according to claim 1, wherein the method comprises the following steps: the solvothermal reaction conditions in step (3) must be at a temperature of 150 ℃ for 24 hours.
5. The method for preparing the trimetallic organic framework-derived iron-nickel alloy/porous carbon composite material according to claim 1, wherein the method comprises the following steps: after the solvothermal reaction in the step (4) is finished, repeatedly centrifuging and washing with N, N-dimethylformamide, and repeatedly centrifuging and washing with absolute ethyl alcohol to obtain a precipitate.
6. The method for preparing the trimetallic organic framework-derived iron-nickel alloy/porous carbon composite material according to claim 1, wherein the method comprises the following steps: the specific operation of the step (5) is that the freeze drying time is required to be 24 hours.
7. A trimetallic organic framework-derived iron nickel alloy/porous carbon composite wave absorbing material, characterized in that it is prepared by the method according to any one of claims 1-6.
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