CN113999651B - Nickel-cobalt double-ligand metal organic framework material and preparation method and application thereof - Google Patents
Nickel-cobalt double-ligand metal organic framework material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000003446 ligand Substances 0.000 title claims abstract description 40
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012621 metal-organic framework Substances 0.000 title claims description 41
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000011358 absorbing material Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 25
- 239000013110 organic ligand Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 229910001453 nickel ion Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 16
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 230000009977 dual effect Effects 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- -1 cobalt ion compound Chemical class 0.000 claims description 4
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 150000002816 nickel compounds Chemical class 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000000015 trinitrotoluene Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 239000013384 organic framework Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 230000007246 mechanism Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003760 magnetic stirring Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 12
- 230000010287 polarization Effects 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 8
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 7
- 238000004891 communication Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NUVDSAKVXWKOAW-UHFFFAOYSA-L dichloronickel;ethanol Chemical compound CCO.Cl[Ni]Cl NUVDSAKVXWKOAW-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- AZJQQNWSSLCLJN-UHFFFAOYSA-N 2-ethoxyquinoline Chemical compound C1=CC=CC2=NC(OCC)=CC=C21 AZJQQNWSSLCLJN-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- WJPGSUZQENDAIE-UHFFFAOYSA-L dichloronickel methanol Chemical compound CO.[Ni](Cl)Cl WJPGSUZQENDAIE-UHFFFAOYSA-L 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000005350 ferromagnetic resonance Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a nickel-cobalt double-ligand metal organic frame material, a preparation method and application thereof, which solve the technical problems of single electromagnetic wave absorption mechanism, poor impedance matching and poor absorption effect of the existing material. The invention also provides a preparation method and application thereof. The invention can be used in the field of electromagnetic wave absorbing materials.
Description
Technical Field
The invention relates to an electromagnetic wave absorbing material, in particular to a nickel-cobalt double-ligand metal organic frame material, a preparation method and application thereof.
Background
Along with the rapid development of electronic technology, electromagnetic technology is also rapidly developed, and electromagnetic waves are widely applied to various fields such as scientific research, industrial production, daily life and the like. As a result of the wide variety of electrical and electronic devices used in military, industrial and everyday life, people face serious threats caused by the increase of electromagnetic waves, which are harmful to both the accuracy of the devices and the health of humans.
Meanwhile, with the continuous development of technology, 5G is gradually blended into modern life, and 5G communication is a new generation communication technology with faster transmission speed, larger network capacity and shorter time delay, and will be widely applied in the near future. The method promotes the rapid development of electronic communication equipment, global positioning system and portable wearable technology to meet the requirements of intellectualization, instantaneity and safety of next generation transmission information communication, according to the prior art, the most possible working frequency bands of 5G telecommunication are 3.3-4.2 GHz, 4.5-5.0 GHz and millimeter wave frequency band (mainly 28 GHz), and in military application, the efficient absorption of radar signals (electromagnetic waves in GHz frequency band, especially electromagnetic waves in x-band) is widely regarded as the key for guaranteeing stealth performance of a fighter. The key to solve the challenge is to develop a material capable of absorbing electromagnetic waves, namely a wave absorbing material, which is one of key materials in the technical fields of national defense and military industry and civil industry, such as military stealth, microwave darkrooms, microwave communication, electromagnetic information leakage protection, electromagnetic interference protection, electromagnetic radiation protection and the like.
In general, electromagnetic wave absorbing materials can be classified into three categories according to loss mechanisms: dielectric loss absorbing materials and magnetic loss absorbing materials, and composite materials of two loss materials, wherein for dielectric loss type wave absorbing materials, electromagnetic waves are lost and absorbed through interfacial polarization or dipole polarization among materials, wherein electromagnetic wave loss mechanisms comprise molecular polarization, ion polarization, interfacial polarization, dielectric polarization and the like, and dielectric loss generally comprises conductive loss, interfacial polarization, dipole polarization and the like. For example, carbon nanotubes, graphene and the like are typical dielectric loss type materials, in addition, for a magnetic loss type wave absorbing material, a wave absorbing mechanism mainly depends on ferromagnetic resonance, eddy current effect and the like to attenuate electromagnetic waves, such as the most common ferrite material, and the most traditional wave absorbing material which is widely used due to the fact that the materials are rich, the cost is low, and the absorption effect is poor due to the fact that the absorption mechanism of the two absorption materials is single, and the impedance matching property of the two absorption materials is poor.
Disclosure of Invention
The invention provides a nickel-cobalt dual-ligand metal organic frame material, a preparation method and application thereof, and aims to solve the technical problems of single electromagnetic wave absorption mechanism, poor impedance matching and poor absorption effect of the existing material.
Therefore, the invention provides a nickel-cobalt double-ligand metal organic frame material which is of a core-shell double-layer structure, wherein the core-shell double-layer structure comprises a core and a shell, the core is a cobalt-based metal organic frame material, and the shell is a nickel-based organic frame material.
The invention also provides a preparation method of the nickel-cobalt double-ligand metal organic framework material, which comprises the following steps: (1) Cobalt ion compounds are used as metal ions, miaow organic ligands are used as organic ligands, and cobalt-based metal organic framework materials are formed through coordination in a solvent and serve as inner nuclear shells of the bimetallic organic framework materials; (2) Selecting a solvent, preparing a seed solution containing nickel ions, and placing a cobalt-based metal organic framework material into the seed solution to obtain a cobalt-based metal organic framework material of a nickel ion-containing seed layer; (3) Using toluene organic ligand as organic ligand, dissolving cobalt-based metal organic frame material of nickel-ion-containing seed layer obtained in the step (2) and the organic ligand in dispersion liquid to form mixed liquid, pouring into a reaction kettle for reaction, and obtaining nickel-cobalt double-ligand metal organic frame material precursor; (4) And (3) heating the nickel-cobalt dual-ligand metal organic framework material precursor obtained in the step (3) in the mixed gas atmosphere, and cooling to room temperature to obtain the nickel-cobalt dual-ligand metal organic framework material.
Preferably, in the step (1), the cobalt ion compound is one of cobalt nitrate hexahydrate, cobalt sulfate heptahydrate, cobalt chloride hexahydrate or a mixture thereof. The cobalt ion compound is dissolved in absolute methanol, water or a mixture thereof, and the concentration range is 0.025mol/L to 0.05mol/L; the miaow class organic ligand is dissolved in absolute methanol, water or a mixture thereof, and the concentration range is 0.4mol/L to 0.8mol/L. The miaow organic ligand is one of dimethyl imidazole, ethoxyquinoline and benzimidazole or a mixture thereof. Slowly adding the dimethyl imidazole solution into the cobalt nitrate hexahydrate solution under the condition of keeping magnetic stirring, then keeping the magnetic stirring at 300-450 r/min for 8-20 minutes, sealing and standing for 15-25 hours; the solvent used for centrifugation is methanol/ethanol, and the mixture is washed for 1 to 3 times and finally dried for 5 to 15 hours at the temperature of 60 to 90 ℃.
Preferably, in the step (2), the solvent is one of ethanol, methanol and deionized water or a mixture thereof, and the mass ratio of the cobalt-based metal organic framework material to the nickel compound in the seed solution is 1 (0.5-2). Adding cobalt-based MOF after nickel chloride solution is formed, and stirring for 10-30 minutes to obtain cobalt-based MOF of the nickel-ion-containing seed layer, wherein the ultrasonic time is 10-30 minutes.
Preferably, in the step (3), the toluene-based organic ligand is one of mesitylene, trinitrotoluene, xylene or a mixture thereof. The molar ratio of toluene organic ligand to nickel compound is 1 (1-3). The ionized water and DMF are used as dispersion liquid, the magnetic stirring speed of the dispersion liquid in the inner container of the reaction kettle is 300-500 r/min, and the stirring time is 20-45 minutes; carrying out hydrothermal reaction for 9-14 hours at 100-170 ℃ in a blast oven; the centrifugal speed is 5000-9000 r/min during post-treatment, the solvent used for centrifugation is ethanol/ionized water, the washing is carried out for 1-3 times, and finally the drying is carried out for 7-14 hours at 60-90 ℃.
Preferably, the product obtained in the step (3) is heated to 500-800 ℃ at 2-10 ℃/min under the atmosphere of argon/nitrogen/argon-hydrogen mixed gas, and is kept for 1-3 hours, and is cooled to room temperature overnight to obtain the carbonized MOF derivative.
The invention also provides application of the nickel-cobalt double-ligand metal organic framework material as an electromagnetic shielding material.
Preferably, the application of the nickel-cobalt double-ligand metal organic frame material as the electromagnetic shielding material fills the nickel-cobalt double-ligand metal organic frame material into resin or paraffin, and the nickel-cobalt double-ligand metal organic frame material is smeared on the surface of an object to form a coating, wherein the thickness of the coating is 1.13-3.35 mm, and the nickel-cobalt double-ligand metal organic frame material accounts for 40-50% of the total weight of the coating.
The invention has the following beneficial effects:
(1) According to the invention, a mode of designing a metal organic framework Material (MOF) structure is adopted, MOF precursors with different morphologies are designed by controlling the proportion of the second ligand to nickel, and then the precursor is carbonized in a reducing atmosphere to obtain the novel MOF derivative. According to the invention, as the magnetic loss of the magnetic metal core, the dielectric loss of the carbon shell with a unique porous structure and the multiple interface polarization and dipole polarization between the two components, the electromagnetic wave absorption performance of the composite material, such as the minimum reflection loss value and the bandwidth range, are greatly enhanced compared with the traditional wave absorption filler with a single absorption mechanism;
(2) The invention achieves the morphology control of the precursor MOF by adjusting the proportion of the double ions and the double ligands, and can change from sea urchin shape to rod shape and flower shape, thereby adjusting the dielectric loss performance of the precursor MOF to achieve the effect of adjusting the wave absorbing performance.
Drawings
FIG. 1 is a diagram of a zwitterionic dual-ligand MOF-1:1 prepared in example 2 of the present invention; magnification factor: 15000 times;
FIG. 2 is a diagram of a zwitterionic dual-ligand MOF-1:1 prepared in example 2 of the present invention; magnification factor: 30000 times.
Detailed Description
The invention is further described below with reference to examples.
Example 1
1) Cobalt nitrate hexahydrate is used as a metal ion, dimethyl imidazole is used as an organic ligand, and a cobalt-based MOF is formed through coordination in a methanol solvent, namely, the cobalt-based MOF is obtained through magnetic stirring for a period of time and standing for a plurality of hours, so that the cobalt-based MOF is used as an inner nuclear shell layer of the double MOFs;
1.1488g of cobalt nitrate hexahydrate was added to 80ml of absolute methanol as a solution A (concentration: 0.05 mol/L); 5.1904g of dimethylimidazole was added to 80ml of absolute methanol as a B solution (concentration: 0.8 mol/L); the solution of dimethylimidazole is slowly added into the solution of cobalt nitrate hexahydrate under the magnetic stirring of 100r/min, then the solution is stirred for 12 minutes under the magnetic stirring of 360r/min, the solvent is ethanol for centrifugation, the solution is washed for 3 times, and finally the solution is dried for 12 hours at 60 ℃.
2) And preparing an ethanol seed solution containing nickel ions by taking absolute ethanol as a solvent according to the mass ratio of the cobalt-based MOF to the nickel chloride hexahydrate of 1:1, adding the cobalt-based MOF after the nickel chloride ethanol solution is formed, carrying out ultrasonic treatment on the weighed cobalt-based MOF in the solution for 25 minutes, and stirring for 10 minutes to obtain the cobalt-based MOF of the nickel ion-containing seed layer.
Example 2
1) Cobalt chloride hexahydrate is used as a metal ion, benzimidazole is used as an organic ligand, and a cobalt-based MOF is formed through coordination in a methanol solvent, namely, the cobalt-based MOF is obtained through magnetic stirring for a period of time and standing for a plurality of hours, so that the cobalt-based MOF is used as an inner nuclear shell layer of the double MOFs;
0.4759g of cobalt chloride hexahydrate was added to 60ml of absolute methanol as a solution A (concentration: 0.025 mol/L); 3.7390g of benzimidazole was added to 50ml of absolute methanol as a B solution (concentration: 0.4 mol/L); the solution of dimethylimidazole was slowly added to the solution of cobalt nitrate hexahydrate with magnetic stirring maintained, followed by stirring for 8 minutes with magnetic stirring at 300r/min, centrifuging using methanol as the solvent, and washing 3 times, and finally drying at 60 ℃ for 15 hours.
2) And preparing a nickel ion-containing seed solution by taking deionized water as a solvent according to the mass ratio of the cobalt-based MOF to the nickel chloride hexahydrate of 2:1, adding the cobalt-based MOF after the nickel chloride solution is formed, carrying out ultrasonic treatment on the weighed cobalt-based MOF in the solution for 10 minutes, and stirring for 30 minutes to obtain the cobalt-based MOF of the nickel ion-containing seed layer.
3) 45Ml of dispersion was prepared and filled into a 100ml reactor liner, wherein ethanol: deionized water: dmf=1:1:1; adding the obtained cobalt-based MOF of the nickel-ion-containing seed layer and 0.084g of mesitylene into the dispersion liquid, wherein the mol ratio of the mesitylene to the nickel chloride hexahydrate is 1:1; the magnetic stirring rotating speed of the dispersion liquid in the inner container of the reaction kettle is 300r/min, and the stirring time is 20 minutes; putting the reaction kettle into a blast oven, and carrying out hydrothermal reaction for 9 hours at 170 ℃; after the product is cooled, the product is subjected to centrifugal treatment, the centrifugal rotation speed is 5000r/min, the solvent used for centrifugation is deionized water, the product is washed for 2 times, and finally the product is filtered by suction and dried for 14 hours at 60 ℃. Thereby obtaining the sea urchin-shaped double-ion double-ligand MOF precursor.
4) The carbonized MOF derivative is prepared by heating to 500 ℃ at 10 ℃/min under the atmosphere of argon/hydrogen gas mixture, preserving heat for 1 hour, and cooling to room temperature overnight.
5) The electromagnetic parameters of the nickel cobalt dual ligand MOF derivatives were tested in the 2-18GHz range, and the prepared MOF derivatives were dispersed in a resin matrix, and when the filling amount was 40%, the material thickness was 1.13mm, and the optimal reflection loss was-50.2 dB.
Example 3
1) Cobalt sulfate heptahydrate is used as metal ion, dimethyl imidazole is used as organic ligand, and cobalt-based MOF is formed through coordination in deionized water solvent, namely cobalt-based MOF is obtained through magnetic stirring for a period of time and standing for a plurality of hours, so that the cobalt-based MOF is used as an inner nuclear shell layer of double MOFs;
1.1100g of cobalt sulfate heptahydrate was added to 80ml of deionized water as solution A (concentration: 0.05 mol/L); 2.5952g of dimethylimidazole was added to 80ml of deionized water as solution B (concentration: 0.4 mol/L); the solution of dimethylimidazole was slowly added to the solution of cobalt nitrate hexahydrate with magnetic stirring maintained, followed by stirring for 12 minutes with 360r/min magnetic stirring, centrifugation using ethanol as the solvent, and washing 2 times, and finally drying at 70 ℃ for 9 hours.
2) And preparing an ethanol seed solution containing nickel ions by taking absolute ethanol as a solvent according to the mass ratio of the cobalt-based MOF to the nickel chloride hexahydrate of 1:1, adding the cobalt-based MOF after the nickel chloride ethanol solution is formed, carrying out ultrasonic treatment on the weighed cobalt-based MOF in the solution for 20 minutes, and stirring for 10 minutes to obtain the cobalt-based MOF of the nickel ion-containing seed layer.
3) Preparation of 60ml of dispersion was loaded into a 100ml reactor liner, wherein ethanol: deionized water: dmf=1:1:1; adding the obtained cobalt-based MOF of the nickel ion-containing seed layer and 0.037g of xylene into the dispersion liquid, wherein the molar ratio of the xylene to the nickel chloride hexahydrate is 1:2; the magnetic stirring rotating speed of the dispersion liquid in the inner container of the reaction kettle is 420r/min, and the stirring time is 35 minutes; putting the reaction kettle into a blast oven, and carrying out hydrothermal reaction for 10 hours at 130 ℃; after the product is cooled, the product is subjected to centrifugal treatment at a centrifugal speed of 8500r/min, the solvent used for centrifugation is ethanol, and the product is washed for 2 times, finally the product is filtered by suction and dried for 9 hours at 70 ℃. Thus obtaining the rod-shaped double-ion double-ligand MOF precursor with better dispersibility.
4) The carbonized MOF derivative is prepared by heating to 700 ℃ at 2 ℃/min under the condition of an argon atmosphere, preserving heat for 2 hours, and cooling to room temperature overnight.
5) The electromagnetic parameters of the nickel cobalt dual ligand MOF derivatives were tested in the 2-18GHz range, and the prepared MOF derivatives were dispersed in paraffin matrix, and when the filling amount was 50%, the material thickness was 3.35mm, and the optimal reflection loss was-41.6 dB.
Example 4
1) Cobalt nitrate hexahydrate is used as a metal ion, dimethyl imidazole is used as an organic ligand, and a cobalt-based MOF is formed through coordination in a methanol solvent, namely, the cobalt-based MOF is obtained through magnetic stirring and standing for a plurality of hours, so that the cobalt-based MOF is used as an inner nuclear shell layer of the double MOFs;
1.1488g of cobalt nitrate hexahydrate was added to 100ml of anhydrous methanol as a solution A (concentration: 0.05 mol/L); 5.1904g of dimethylimidazole was added to 100ml of absolute methanol as a B solution (concentration: 0.8 mol/L); the solution of dimethylimidazole was slowly added to the solution of cobalt nitrate hexahydrate with maintained magnetic stirring, followed by stirring for 20 minutes with 450r/min magnetic stirring, centrifuging using solvents ethanol and methanol, and washing 1 time each, and finally drying at 90 ℃ for 5 hours.
2) Preparing a nickel ion-containing methanol seed solution by taking anhydrous methanol as a solvent according to the mass ratio of cobalt-based MOF to nickel chloride hexahydrate of 1:2, adding the cobalt-based MOF after the nickel chloride methanol solution is formed, carrying out ultrasonic treatment on the weighed cobalt-based MOF in the solution for 30 minutes, and stirring for 20 minutes to obtain the cobalt-based MOF of the nickel ion-containing seed layer.
3) 75Ml of dispersion was prepared and filled into a 100ml reactor liner, wherein ethanol: deionized water: dmf=1:1:1; adding the obtained cobalt-based MOF of the nickel ion-containing seed layer and 0.053g of trinitrotoluene into the dispersion liquid, wherein the mol ratio of the trinitrotoluene to the nickel chloride hexahydrate is 1:3; the magnetic stirring rotating speed of the dispersion liquid in the inner container of the reaction kettle is 500r/min, and the stirring time is 45 minutes; putting the reaction kettle into a blast oven, and carrying out hydrothermal reaction for 14 hours at 100 ℃; after the product is cooled, the product is subjected to centrifugal treatment, the centrifugal rotation speed is 9000r/min, the solvents used in the centrifugation are ethanol and deionized water, the washing is carried out for 1 time, and finally the product is filtered by suction and dried for 7 hours at 90 ℃. Thereby obtaining petal-shaped and part rod-shaped dual-ion dual-ligand MOF precursor.
4) The carbonized MOF derivative is prepared by heating to 800 ℃ at 5 ℃/min under the nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature overnight.
5) The electromagnetic parameters of the nickel cobalt dual ligand MOF derivatives were tested in the 2-18GHz range, and the prepared MOF derivatives were dispersed in a resin matrix, and when the filling amount was 40%, the material thickness was 1.59mm, and the optimal reflection loss was-55.6 dB.
Comparative example
1) Cobalt nitrate hexahydrate is used as a metal ion, dimethyl imidazole is used as an organic ligand, and a cobalt-based MOF is formed through coordination in a methanol solvent, namely, the cobalt-based MOF is obtained through magnetic stirring for a period of time and standing for a plurality of hours, so that the cobalt-based MOF is used as an inner nuclear shell layer of the double MOFs;
1.1488g of cobalt nitrate hexahydrate was added to 80ml of absolute methanol as solution A; 2.5952g of dimethylimidazole was added to 80ml of absolute methanol as solution B; the solution of dimethylimidazole is slowly added into the solution of cobalt nitrate hexahydrate under the magnetic stirring of 100r/min, then the solution is stirred for 12 minutes under the magnetic stirring of 360r/min, the solvent is ethanol for centrifugation, the solution is washed for 3 times, and finally the solution is dried for 12 hours at 60 ℃.
2) The carbonized MOF derivative is prepared by heating to 800 ℃ at 5 ℃/min under the nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature overnight.
3) The electromagnetic parameters of the nickel cobalt dual ligand MOF derivatives were tested in the 2-18GHz range, and the prepared MOF derivatives were dispersed in paraffin matrix, and when the filling amount was 40%, the material thickness was 3.15mm, and the optimal reflection loss was only-10.3 dB.
However, the foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, so that the substitution of equivalent elements or equivalent variations and modifications within the scope of the invention are intended to fall within the scope of the claims.
Claims (7)
1. The preparation method of the nickel-cobalt double-ligand metal organic frame material is characterized in that the nickel-cobalt double-ligand metal organic frame material is of a core-shell double-layer structure, the core-shell double-layer structure comprises a core and a shell, the core is a cobalt-based metal organic frame material, and the shell is a nickel-based organic frame material;
The nickel-cobalt double-ligand metal organic framework material is prepared by adopting a method comprising the following steps of:
(1) Cobalt ion compounds are used as metal ions, miaow organic ligands are used as organic ligands, and cobalt-based metal organic framework materials are formed through coordination in a solvent and serve as inner nuclear shells of the bimetallic organic framework materials; the cobalt ion compound is one of cobalt nitrate hexahydrate, cobalt sulfate heptahydrate and cobalt chloride hexahydrate or a mixture thereof; the miaow organic ligand is one of dimethyl imidazole and benzimidazole or a mixture thereof;
(2) Selecting a solvent, preparing a seed solution containing nickel ions, and placing a cobalt-based metal organic framework material into the seed solution to obtain a cobalt-based metal organic framework material of a nickel ion-containing seed layer;
(3) Using toluene organic ligand as organic ligand, dissolving cobalt-based metal organic frame material of nickel-ion-containing seed layer obtained in the step (2) and the organic ligand in dispersion liquid to form mixed liquid, pouring into a reaction kettle for reaction, and obtaining nickel-cobalt double-ligand metal organic frame material precursor; the toluene organic ligand is one of mesitylene, trinitrotoluene and xylene or a mixture thereof;
(4) And (3) heating the nickel-cobalt dual-ligand metal organic framework material precursor obtained in the step (3) in the mixed gas atmosphere, and cooling to room temperature to obtain the nickel-cobalt dual-ligand metal organic framework material.
2. The method for preparing a nickel-cobalt dual ligand metal organic framework material according to claim 1, comprising the steps of, in the step (1), dissolving the cobalt ion compound in anhydrous methanol, water or a mixture thereof, wherein the concentration range is 0.025mol/L to 0.05mol/L; the miaow class organic ligand is dissolved in absolute methanol, water or a mixture thereof, and the concentration range is 0.4mol/L to 0.8mol/L.
3. The method for preparing a nickel-cobalt dual ligand metal organic framework material according to claim 1, wherein in the step (2), the solvent is one of ethanol, methanol and deionized water or a mixture thereof, and the mass ratio of the cobalt-based metal organic framework material to the nickel compound in the seed solution is 1 (0.5-2).
4. The method for producing a nickel-cobalt dual ligand metal organic framework material according to claim 1, comprising the steps of, in the step (3), the molar ratio of toluene-based organic ligand to nickel compound
The ratio is 1 (1-3).
5. A nickel cobalt dual ligand metal organic framework material produced using the method of any one of claims 1 to 4.
6. The use of the nickel cobalt dual ligand metal organic framework material according to claim 5 as an electromagnetic wave absorbing material.
7. The use of the nickel-cobalt double-ligand metal organic frame material as electromagnetic wave absorbing material according to claim 6, wherein the nickel-cobalt double-ligand metal organic frame material is filled into resin or paraffin, and is smeared on the surface of an object to form a coating, the thickness of the coating is 1.13-3.35 mm, and the nickel-cobalt double-ligand metal organic frame material accounts for 40-50% of the total weight of the coating.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885784A (en) * | 2016-04-18 | 2016-08-24 | 青岛大学 | Preparation method of wave-absorbing material adopting core-shell structure |
| CN111330639A (en) * | 2020-04-09 | 2020-06-26 | 安徽师范大学 | Hybrid material of porous cobalt-zinc core-shell metal organic framework compound confinement noble metal nanoparticles and preparation method and application thereof |
| CN111515409A (en) * | 2020-04-08 | 2020-08-11 | 大连理工大学 | Preparation method of carbon-coated magnetic nickel-cobalt core-shell structure microspheres |
| CN113173605A (en) * | 2021-04-27 | 2021-07-27 | 西北工业大学 | Core-shell type metal sulfide composite material and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885784A (en) * | 2016-04-18 | 2016-08-24 | 青岛大学 | Preparation method of wave-absorbing material adopting core-shell structure |
| CN111515409A (en) * | 2020-04-08 | 2020-08-11 | 大连理工大学 | Preparation method of carbon-coated magnetic nickel-cobalt core-shell structure microspheres |
| CN111330639A (en) * | 2020-04-09 | 2020-06-26 | 安徽师范大学 | Hybrid material of porous cobalt-zinc core-shell metal organic framework compound confinement noble metal nanoparticles and preparation method and application thereof |
| CN113173605A (en) * | 2021-04-27 | 2021-07-27 | 西北工业大学 | Core-shell type metal sulfide composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| A novel Co/TiO 2 nanocomposite derived from a metal–organic framework: synthesis and efficient microwave absorption;ZHANG X等;《 Journal of Materials Chemistry C》;第4卷;1860-1870 * |
| Conducting polymer coated metal-organic framework nanoparticles: facile synthesis and enhanced electromagnetic absorption properties;WANG Y等;《Synthetic Metals》;第228卷;18-24 * |
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