CN116410476B - Bi-MOF derivative material and method for enhancing wave absorbing performance and structural stability of bi-MOF derivative material - Google Patents
Bi-MOF derivative material and method for enhancing wave absorbing performance and structural stability of bi-MOF derivative material Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 111
- 239000012621 metal-organic framework Substances 0.000 claims description 66
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000004570 mortar (masonry) Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
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- 229920001661 Chitosan Polymers 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
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- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
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- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OHVGNSMTLSKTGN-BTVCFUMJSA-N [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O OHVGNSMTLSKTGN-BTVCFUMJSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The application discloses a bi-MOF derivative material and a method for enhancing the wave absorbing performance and structural stability of the bi-MOF derivative material. The method comprises the following steps: dissolving a carbon-containing precursor and FeCl 3·6H2 O in a first organic solvent, and uniformly dispersing; adding bi-MOF derivative materials, uniformly stirring, filtering and separating a product to obtain a first solid, washing the first solid by adopting a first organic solvent, and then grinding and drying to obtain a hybrid substance; and carrying out high-temperature treatment on the hybrid substance to obtain the bi-MOF derivative material with enhanced wave absorbing performance and structural stability. By applying the technical scheme of the application, the good synergistic effect between the magnetic metal ions and the small molecular organic matters has obvious effect on enhancing the magnetic performance and structural stability of the MOF derivative material, and the increase of the contents of the carbon material and the magnetic metal/corresponding oxide after heat treatment has obvious improvement on the electromagnetic shielding wave absorbing performance of the MOF derivative material.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a bi-MOF derivative material and a method for enhancing the wave absorbing performance and structural stability of the bi-MOF derivative material.
Background
Electromagnetic interference and electromagnetic radiation cause great trouble to human life, so that the development of a lightweight high-efficiency electromagnetic interference shielding material is particularly important. The metal organic framework compound (Metal Organic Framework, MOF) is a novel crystalline material with a porous structure constructed by metal center ions and organic ligands, and has a very large specific surface area, so that the wave-absorbing material can be designed and prepared according to requirements. The MOF derivative is a series of metal/metal compound and porous carbon composite materials obtained by heat treatment under inert atmosphere, the MOF derivative is easy to cause the loss of structural stability due to excessive consumption of carbon materials in the heat treatment process, and poor wave absorption performance is caused by a weak electromagnetic loss mechanism at low frequency, so that the MOF derivative porous materials are the problems to be overcome in the use of the MOF derivative porous materials as wave absorption materials.
At present, most of MOF related electromagnetic wave absorbing materials adopt metal nodes with magnetic metal ions as MOF structures to be combined with organic ligands, the content of derived carbon materials in the final product can be improved by changing the types of the organic ligands, but macromolecular organic ligands are difficult to be suitable for various magnetic metals and to construct various MOF structures, and the MOF derived materials are still weak in low-frequency wave absorbing performance.
Disclosure of Invention
The invention aims to provide a bi-MOF derivative material and a method for enhancing the wave absorbing performance and structural stability of the bi-MOF derivative material so as to enhance the wave absorbing performance and structural stability of the bi-MOF derivative material.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for enhancing the wave absorbing performance and structural stability of a bi-MOF derived material. The method comprises the following steps: dissolving a carbon-containing precursor and FeCl 3·6H2 O in a first organic solvent, and uniformly dispersing to obtain a first mixed solution; adding bi-MOF derivative materials into a first mixed solution, uniformly stirring, filtering and separating a product to obtain a first solid, washing the first solid by adopting a first organic solvent, and then grinding and drying to obtain a hybrid substance; and carrying out high-temperature treatment on the hybrid substance to obtain the bi-MOF derivative material with enhanced wave absorbing performance and structural stability.
Further, the high temperature treatment of the hybrid substance includes: the hybridized material is placed in a tube furnace for high temperature treatment, the temperature is raised to 600-800 ℃ at the heating rate of 2-5 ℃/min, and the temperature is kept for 1-3h.
Further, the carbon-containing precursor is one or more of glucose, chitosan, urea or ethylcellulose; preferably, the first organic solvent is ethanol and/or methanol; preferably, the content of the carbon-containing precursor in the first mixed solution is 15-30 mg/mL; the content of FeCl 3·6H2 O is 30-60mg/mL.
Further, the bi-MOF derivative material is added to the first mixed solution in an amount of 20-30mg/mL.
Further, the condition of drying the first solid is 50-70 ℃ for 10-15 hours; preferably 60℃for 12 hours.
Further, the bi-MOF derivative material is prepared by the following steps: s1, mixing Co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O) and adding the mixture into methanol or N.N-dimethylformamide to prepare a dispersion liquid A, dissolving 2-methylimidazole into the methanol to prepare a dispersion liquid B, S2, mixing the dispersion liquid A and the dispersion liquid B, stirring the mixture for 18 to 24 hours at room temperature, centrifugally separating out a second solid, and washing the second solid with the methanol for 3 to 5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, namely the bi-MOF derivative material.
Further, the method further comprises: and (3) placing the obtained ZIF8@ZIF67 bimetallic MOF structure in a vacuum oven to dry for 12-15 hours at 60 ℃, and grinding the collected product uniformly by using a mortar.
Further, S1 includes: co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O) are mixed and added into methanol, and the mixture is mechanically stirred for 1 to 2 hours at room temperature to prepare a dispersion A, wherein the molar ratio of Co (NO 3)2·6H2 O to Zn (NO 3)2·6H2 O is 1:1) is preferable.
Further, the mixing ratio of the dispersion A and the dispersion B was m (2-methylimidazole) m (Co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O) =1:1) in terms of the mass ratio of 2-methylimidazole and Co (NO 3)2·6H2 O to Zn (NO 3)2·6H2 O), preferably, co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O) in total concentration in methanol was 0.06 to 0.1mmol/mL, preferably, the concentration of 2-methylimidazole in methanol was 30 to 50mg/mL in the dispersion B.
According to another aspect of the present application, there is provided a bi-MOF derived material. The bi-MOF derived material is treated by any of the methods of the application described above.
By applying the technical scheme of the application, a simple solution impregnation process is actually adopted, magnetic metal ions and small molecular organic matters are reintroduced into the outer surface of the MOF structure, and the good synergistic effect between the magnetic metal ions and the small molecular organic matters has obvious effects on enhancing the magnetic performance and structural stability of the MOF derivative material, and the increase of the contents of the carbon material and the magnetic metal/corresponding oxide after heat treatment has obvious improvement on the electromagnetic shielding wave absorbing performance of the MOF derivative material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
Fig. 1 shows a schematic flow chart of a preparation method of a bi-MOF derivative material with enhanced wave absorbing performance and structural stability according to an embodiment of the present invention.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
Aiming at the technical problems that the organic ligand described in the background art is difficult to be suitable for various magnetic metals and various MOF structures are constructed, and the MOF derivative material is still very weak in the aspect of low-frequency wave absorption performance, the application provides the following technical scheme.
According to an exemplary embodiment of the present invention, a method for enhancing the wave absorbing properties and structural stability of bi-MOF derived materials is provided. The method comprises the following steps: dissolving a carbon-containing precursor or a plurality of carbon-containing precursors and FeCl 3·6H2 O in a first organic solvent to uniformly disperse to obtain a first mixed solution; adding bi-MOF derivative materials into a first mixed solution, uniformly stirring, filtering and separating a product to obtain a first solid, washing the first solid in a first organic solvent, and then grinding and drying to obtain a hybrid substance; and carrying out high-temperature treatment on the hybrid substance to obtain the bi-MOF derivative material with enhanced wave absorbing performance and structural stability.
By applying the technical scheme of the application, a simple solution impregnation process is actually adopted, magnetic metal ions and small molecular organic matters are reintroduced into the outer surface of the MOF structure, and the good synergistic effect between the magnetic metal ions and the small molecular organic matters has obvious effects on enhancing the magnetic performance and structural stability of the MOF derivative material, and the increase of the content of the carbon material (carbon-containing precursor is converted into carbon nano tubes after high-temperature treatment) and the magnetic metal/corresponding oxide after heat treatment has obvious improvement on the electromagnetic shielding wave absorbing performance of the MOF derivative material.
Preferably, the high temperature treatment of the hybrid substance comprises: the hybridized material is placed in a tube furnace for high temperature treatment, the temperature is raised to 600-800 ℃ at the heating rate of 2-5 ℃/min, and the temperature is kept for 1-3h. In the actual production process, the expected effect can be primarily achieved after heat preservation for 1h, but in order to ensure that organic matters can be thoroughly converted into carbon materials in high-temperature treatment, the heat treatment temperature or the heat preservation time can be properly selected and increased.
The carbon-containing precursor can be converted into a carbon material after pyrolysis treatment, and in a preferred embodiment of the application, the carbon-containing precursor is one or more of glucose, chitosan, urea or ethylcellulose; preferably, the first organic solvent is ethanol and/or methanol; the content of the carbon-containing precursor in the first mixed solution is 15-30 mg/mL; the content of FeCl 3·6H2 O is 30-60mg/mL, so that the content of magnetic metal particles and carbon nano tubes in the final product is controlled, and the wave absorbing performance and structural stability of the bi-MOF derivative material are enhanced.
In a preferred embodiment of the present invention, the conditions for drying the first solid are 50 to 70 ℃ for 10 to 15 hours; preferably 60 c for 12 hours to ensure adequate drying of the first solid, as insufficient drying may have an effect on weighing or dosing in subsequent experiments.
According to an exemplary embodiment of the present invention, a bi-MOF derived material is prepared by: s1, mixing Co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O) and adding into methanol to prepare a dispersion liquid A, dissolving 2-methylimidazole into methanol to prepare a dispersion liquid B, S2, mixing the dispersion liquid A and the dispersion liquid B, stirring for 24 hours at room temperature, centrifugally separating out a second solid, and washing with methanol for 3-5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, namely a bi-MOF derivative material.
Preferably, the method further comprises: and (3) placing the obtained ZIF8@ZIF67 bimetallic MOF structure in a vacuum oven to dry for 12 hours at 60 ℃, and grinding the collected product uniformly by using a mortar. Further, S1 includes: co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O) are mixed and added into methanol or N.N-dimethylformamide, and the mixture is mechanically stirred for 1 to 2 hours at room temperature, so that the additive is completely dissolved in the methanol or the N.N-dimethylformamide to prepare a dispersion liquid A, and preferably, co (NO 3)2·6H2 O and Zn (the mol ratio of NO 3)2·6H2 O is 1:1).
Preferably, co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O total concentration in methanol is 0.06-0.1mmol/mL; 2-methylimidazole concentration in methanol is 30-50 mg/mL) is present in dispersion A.
According to an exemplary embodiment of the present invention, a bi-MOF derived material is provided. The bi-MOF derivative material is obtained by processing any one of the methods.
In a preferred embodiment of the present invention, the preparation method for enhancing the wave absorbing performance and the structural stability of the bi-MOF derivative material is shown in FIG. 1, and comprises the following steps: (1) 6mmol Co (NO 3)2·6H2 O and 6mmolZn (NO 3)2·6H2 O) are mixed and added into 80mL of methanol, and the mixture is mechanically stirred for 1h at room temperature, and 3.7g of 2-methylimidazole is dissolved into 80mL of methanol, and the stirring is continued for 1h until the mixture is uniformly dispersed; mixing two dispersed liquid phases, stirring for 24 hours at room temperature, centrifugally separating, washing with methanol for 3-5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, placing in a vacuum oven, drying at 60 ℃ for 12 hours, grinding the collected product uniformly by a mortar, 3 dissolving 0.5g glucose/chitosan/urea/ethylcellulose and 1g FeCl 3·6H2 O in 20mL ethanol for uniform dispersion, taking 0.5g bi-MOF, adding into the mixed solution, stirring uniformly, filtering to separate the product, washing with ethanol for several times, properly heating and drying, grinding in a mortar, placing in a vacuum oven for drying at 60 ℃ for 12 hours, placing in a tube furnace for high-temperature treatment, heating up to 600-800 ℃ at a heating rate of 2 ℃/min, preserving heat for 1-3 hours to obtain a final product C-bi-MOF-Fe-glu, finally uniformly blending the product with 10wt%/20wt%/30wt% filling amount with paraffin, preparing a concentric ring with an inner diameter of 7.00mm, and performing electromagnetic vector performance test by using a die to prepare a concentric ring with an outer diameter of 3.04 mm.
According to the technical scheme, the method realizes that iron ions and small molecular organic matters are simply and effectively coated on the surface of the bi-MOF through a solution impregnation process. Because the bi-MOF material is internally provided with a porous structure, and metal ions used for impregnating and loading can form a stable complex with nitrogen atoms in the organic ligand dimethyl imidazole at normal temperature, the solution impregnation can enable iron ions to be simply and effectively uniformly attached to the outer surface and the pore canal of the bi-MOF structure, so that aggregation of simple substance iron and corresponding compounds generated after heat treatment is avoided, and the dispersion problem is effectively solved. The coating of the glucose layer provides carbon materials required to be consumed in the heat treatment process, so that the consumption of organic ligands can be reduced, and the carbon layer converted after the heat treatment can play a certain role in protecting the framework of the MOF. The structure of the integral material is changed along with the heat treatment process, wherein the metallic zinc is converted into steam along with the heat treatment process to escape, so that a plurality of holes which coexist with the pore canal of the MOF framework are formed; the derivative glucose carbon layer and the original regular dodecahedron structure form a multi-layer structure; in addition, in the heat treatment process, carbon nanotubes are grown on the outer surface of the material in situ under the catalysis of metallic cobalt to construct sea urchin-like morphology. Wherein, the organic ligand and glucose in the composite material are pyrolyzed to form a multi-layer structure and an outer surface sea urchin-like structure, and the formed multi-hole and multi-channel structure increases the multiple reflection of the incident electromagnetic wave, improves the dielectric loss and increases the polarized interface of the incident electromagnetic wave; the introduction of the additional magnetic material increases the magnetic loss, and the coating of the surface carbon layer is beneficial to improving the impedance matching of the incident electromagnetic wave, so that the wave absorption wave band of the material can be effectively expanded to a low-frequency wave band.
The advantageous effects of the present invention will be further described below with reference to examples.
Example 1
A method for enhancing the wave absorbing performance and the structural stability of bi-MOF derivative materials comprises the following steps:
(1) 6mmol of Co (NO 3)2·6H2 O and 6mmol of Zn (NO 3)2·6H2 O are mixed and added into 80mL of methanol, and the mixture is mechanically stirred for 1h at room temperature, and 3.7g of 2-methylimidazole is dissolved into 80mL of methanol, and the mixture is continuously stirred for 1h until the mixture is uniformly dispersed;
(2) Mixing the two dispersed liquid phases, stirring for 24 hours at room temperature, centrifugally separating, washing with methanol for 5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, placing in a vacuum oven, drying at 60 ℃ for 12 hours, and grinding the collected product uniformly by using a mortar;
(3) Dissolving 0.5g of glucose and 1g of FeCl 3·6H2 O in 20mL of ethanol, dispersing uniformly, adding 0.5g of bi-MOF into the mixed solution, stirring uniformly, heating and drying properly, grinding in a mortar, and drying in a vacuum oven at 60 ℃ for 12 hours;
(4) Placing the hybrid substance in a tube furnace for high-temperature treatment, heating to 700 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain a final product C-bi-MOF-Fe-glu; and finally, uniformly blending the product with paraffin in a filling amount of 20wt%, preparing concentric rings with the outer diameter of 7mm and the inner diameter of 3.04mm by adopting a die, and carrying out electromagnetic performance test by using a vector network analyzer.
Example 2
A preparation method for enhancing the wave absorbing performance and structural stability of bi-MOF derivative materials comprises the following steps:
(1) 6mmol of Co (NO 3)2·6H2 O and 6mmol of Zn (NO 3)2·6H2 O are mixed and added into 80mL of methanol, and the mixture is mechanically stirred for 1h at room temperature, and 3.7g of 2-methylimidazole is dissolved into 80mL of methanol, and the mixture is continuously stirred for 1h until the mixture is uniformly dispersed;
(2) Mixing the two dispersed liquid phases, stirring for 24 hours at room temperature, centrifugally separating, washing with methanol for 5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, placing in a vacuum oven, drying at 60 ℃ for 12 hours, and grinding the collected product uniformly by using a mortar;
(3) Dissolving 0.5g of chitosan and 1g of FeCl 3·6H2 O in 20mL of deionized water, uniformly dispersing, adding 0.5g of bi-MOF into the mixed solution, uniformly stirring, properly heating and drying, grinding in a mortar, and drying under the conditions of 60 ℃ in a vacuum oven for 12 hours;
(4) Placing the hybrid substance in a tube furnace for high-temperature treatment, heating to 700 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain a final product C-bi-MOF-Fe-SA; and finally, uniformly blending the product with paraffin in a filling amount of 20wt%, preparing concentric rings with the outer diameter of 7mm and the inner diameter of 3.04mm by adopting a die, and carrying out electromagnetic performance test by using a vector network analyzer.
Example 3
A preparation method for enhancing the wave absorbing performance and structural stability of bi-MOF derivative materials comprises the following steps:
(1) 6mmol of Co (NO 3)2·6H2 O and 6mmol of Zn (NO 3)2·6H2 O are mixed and added into 80mL of methanol, and the mixture is mechanically stirred for 1h at room temperature, and 3.7g of 2-methylimidazole is dissolved into 80mL of methanol, and the mixture is continuously stirred for 1h until the mixture is uniformly dispersed;
(2) Mixing the two dispersed liquid phases, stirring for 24 hours at room temperature, centrifugally separating, washing with methanol for 5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, placing in a vacuum oven, drying at 60 ℃ for 12 hours, and grinding the collected product uniformly by using a mortar;
(3) Dissolving 0.5g of urea and 1g of FeCl 3·6H2 O in 20mL of ethanol, dispersing uniformly, adding 0.5g of bi-MOF into the mixed solution, stirring uniformly, heating and drying properly, grinding in a mortar, and drying in a vacuum oven at 60 ℃ for 12 hours;
(4) Placing the hybrid substance in a tube furnace for high-temperature treatment, heating to 700 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain a final product C-bi-MOF-Fe-urea; and finally, uniformly blending the product with paraffin in a filling amount of 20wt%, preparing concentric rings with the outer diameter of 7mm and the inner diameter of 3.04mm by adopting a die, and carrying out electromagnetic performance test by using a vector network analyzer.
Example 4
A preparation method for enhancing wave absorbing performance and structural stability of MOF derivative materials comprises the following steps:
(1) 6mmol of Co (NO 3)2·6H2 O and 6mmol of Zn (NO 3)2·6H2 O are mixed and added into 40mL of methanol, and the mixture is mechanically stirred for 1h at room temperature, and 3.7g of 2-methylimidazole is dissolved in 10mL of methanol, and the mixture is continuously stirred for 1h until the mixture is uniformly dispersed;
(2) Mixing the two dispersed liquid phases, stirring for 24 hours at room temperature, centrifugally separating, washing with methanol for 5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, placing in a vacuum oven, drying at 60 ℃ for 12 hours, and grinding the collected product uniformly by using a mortar;
(3) Dissolving 1g of ethyl cellulose and 1g of FeCl 3·6H2 O in 20mL of ethanol, dispersing uniformly, adding 0.5g of bi-MOF into the mixed solution, stirring uniformly, heating and drying properly, grinding in a mortar, and placing in a vacuum oven at 60 ℃ for 12h for drying;
(4) Placing the hybrid substance in a tube furnace for high-temperature treatment, heating to 700 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain a final product bi-MOF-Fe-cnc; finally, uniformly blending the product with paraffin wax in a filling amount of 20wt%, preparing concentric rings with an outer diameter of 7mm and an inner diameter of 3.04mm by using a die, and carrying out electromagnetic performance test by using a vector network analyzer, wherein the results are shown in Table 1.
Table 1 the bi-MOF derived composite material obtained in each example has the properties of absorbing waves:
The combination of the carbon material and the magnetic material in the hybrid material effectively improves the magnetic loss and dielectric loss of the material on electromagnetic waves, further improves the absorption performance on the electromagnetic waves, and the materials have good wave absorption performance and effective wave absorption bandwidth, compared with the hybrid material prepared by taking glucose as a carbon source, the effective wave absorption bandwidth (less than-10 dB) can reach 7.3GHz under the thickness condition of only 1.96mm, and the optimal reflection loss can reach-33.5 dB.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A method for enhancing the wave absorbing performance and the structural stability of a bi-MOF derivative material is characterized by comprising the following steps:
dissolving a carbon-containing precursor and FeCl 3·6H2 O in a first organic solvent, and uniformly dispersing to obtain a first mixed solution;
adding bi-MOF derivative materials into the first mixed solution, uniformly stirring, filtering and separating a product to obtain a first solid, washing the first solid by adopting the first organic solvent, and then grinding and drying to obtain a hybrid substance;
Carrying out high-temperature treatment on the hybrid substance to obtain a bi-MOF derivative material with enhanced wave absorbing performance and structural stability;
The bi-MOF derivative material is prepared by the following steps:
S1, mixing Co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O are mixed and added into methanol or N.N-dimethylformamide to prepare a dispersion liquid A, and 2-methylimidazole is dissolved in the methanol to prepare a dispersion liquid B;
S2, mixing the dispersion liquid A and the dispersion liquid B, stirring for 18-24 hours at room temperature, centrifugally separating out a second solid, and cleaning with methanol for 3-5 times to obtain a ZIF8@ZIF67 bimetallic MOF structure, namely the bi-MOF derivative material;
The high temperature treatment of the hybrid substance comprises: the hybridized material is placed in a tube furnace for high-temperature treatment, the temperature is raised to 600-800 ℃ at the heating rate of 2-5 ℃/min, and the temperature is kept for 1-3h.
2. The method of claim 1, wherein the carbon-containing precursor is one or more of glucose, chitosan, urea, or ethylcellulose.
3. The method according to claim 2, wherein the first organic solvent is ethanol and/or methanol.
4. The method according to claim 2, wherein the content of the carbon-containing precursor in the first mixed solution is 15-30 mg/mL; the content of FeCl 3·6H2 O is 30-60mg/mL.
5. The method of claim 1, wherein the bi-MOF derivative material is added to the first mixed solution in an amount of 20-30mg/mL.
6. The method of claim 1, wherein the conditions for drying the first solid are 50-70 ℃ for 10-15 hours.
7. The method of claim 6, wherein the conditions for drying the first solid are 60 ℃ for 12 hours.
8. The method according to claim 1, wherein the method further comprises: and (3) placing the obtained ZIF8@ZIF67 bimetallic MOF structure in a vacuum oven, drying at 60 ℃ for 12-15 hours, and uniformly grinding the collected product by using a mortar.
9. The method according to claim 1, wherein S1 comprises: co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O) are mixed and added into methanol, and the mixture is mechanically stirred for 1 to 2 hours at room temperature, so that the dispersion liquid A is prepared.
10. The method of claim 9, wherein Co (NO 3)2·6H2 O to Zn (NO 3)2·6H2 O molar ratio is 1:1).
11. The method according to claim 1, characterized in that the mixing ratio of the dispersion a and the dispersion B is m (2-methylimidazole) m (Co (NO 3)2·6H2 O to Zn (NO 3)2·6H2 O) =1:1) in terms of 2-methylimidazole and Co (NO 3)2·6H2 O to Zn (NO 3)2·6H2 O) mass ratio.
12. The method according to claim 11, characterized in that the total concentration of Co (NO 3)2·6H2 O and Zn (NO 3)2·6H2 O in methanol) in dispersion a is 0.06-0.1mmol/mL.
13. The method according to claim 12, characterized in that the concentration of 2-methylimidazole in methanol in the dispersion B is 30-50mg/mL.
14. A bi-MOF derived material, characterized by being treated by the method according to any one of claims 1 to 13.
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