CN113999651A - Nickel-cobalt dual-ligand metal-organic framework material and preparation method and application thereof - Google Patents
Nickel-cobalt dual-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 60
- 239000003446 ligand Substances 0.000 title claims abstract description 38
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- 239000000203 mixture Substances 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
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- 238000006243 chemical reaction Methods 0.000 claims description 13
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- 239000007788 liquid Substances 0.000 claims description 11
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- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- -1 cobalt ion compound Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 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
- 239000002355 dual-layer 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
- 239000013384 organic framework Substances 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
- AZJQQNWSSLCLJN-UHFFFAOYSA-N 2-ethoxyquinoline Chemical compound C1=CC=CC2=NC(OCC)=CC=C21 AZJQQNWSSLCLJN-UHFFFAOYSA-N 0.000 claims description 2
- 229910017709 Ni Co Inorganic materials 0.000 claims 3
- 229910003267 Ni-Co Inorganic materials 0.000 claims 3
- 229910003262 Ni‐Co Inorganic materials 0.000 claims 3
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- 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
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- 239000011159 matrix material Substances 0.000 description 4
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- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 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
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- NUVDSAKVXWKOAW-UHFFFAOYSA-L dichloronickel;ethanol Chemical compound CCO.Cl[Ni]Cl NUVDSAKVXWKOAW-UHFFFAOYSA-L 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- 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
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- 241000257465 Echinoidea Species 0.000 description 1
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- WJPGSUZQENDAIE-UHFFFAOYSA-L dichloronickel methanol Chemical compound CO.[Ni](Cl)Cl WJPGSUZQENDAIE-UHFFFAOYSA-L 0.000 description 1
- 230000003203 everyday effect Effects 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
Abstract
The invention relates to a nickel-cobalt dual-ligand metal organic framework material, and a preparation method and application thereof, and solves the technical problems of single electromagnetic wave absorption mechanism, poor impedance matching property 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 absorption materials.
Description
Technical Field
The invention relates to an electromagnetic wave absorbing material, in particular to a nickel-cobalt dual-ligand metal-organic framework material and a preparation method and application thereof.
Background
With the rapid development of electronic technology, electromagnetic technology is also rapidly developing, and electromagnetic waves are widely applied to various fields such as scientific research, industrial production, daily life and the like. Due to the wide use of various electrical and electronic devices in military, industrial and everyday life, people face a serious threat due to the increase of electromagnetic waves, and electromagnetic radiation or pollution is harmful to the precision of the devices and the health of human beings.
Meanwhile, with the continuous development of science and technology, 5G gradually blends 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, a global positioning system and a portable wearable technology so as 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 bands (mainly 28GHz), and in military application, the high-efficiency absorption of radar signals (electromagnetic waves in GHz frequency bands, especially electromagnetic waves in x-wave bands) is widely considered as the key for ensuring the stealth performance of fighters. The key point for solving the challenge is to develop a material capable of absorbing electromagnetic waves, namely the wave-absorbing material, which is one of key materials in the technical fields of national defense, military industry and civil use, such as military stealth, microwave darkroom, microwave communication, electromagnetic information leakage protection, electromagnetic interference protection, electromagnetic radiation protection and the like.
Generally, electromagnetic wave absorbing materials can be classified into three types according to the loss mechanism: the dielectric loss absorbing material and the magnetic loss absorbing material and the composite material of the two loss materials, wherein, for the dielectric loss type wave absorbing material, the electromagnetic wave is lost and absorbed through the interface polarization or dipole polarization between the materials, wherein, the electromagnetic wave loss mechanism comprises molecular polarization, ion polarization, interface polarization, dielectric polarization and the like, and the dielectric loss generally comprises conductive loss, interface polarization, dipole polarization and the like. For example, carbon nanotubes, graphene and the like are typical dielectric loss type materials, and in addition, for magnetic loss type wave-absorbing materials, the wave-absorbing mechanism mainly depends on ferromagnetic resonance, eddy current effect and the like to attenuate electromagnetic waves, for example, the most common ferrite material is the most traditional wave-absorbing material widely used due to abundant raw materials and low cost, and the two absorbing materials have single absorbing mechanism, so that the impedance matching performance is poor, and the absorbing effect is poor.
Disclosure of Invention
The invention provides a nickel-cobalt dual-ligand metal-organic framework material, a preparation method and application thereof, aiming at solving the technical problems of single electromagnetic wave absorption mechanism, poor impedance matching and poor absorption effect of the existing material.
Therefore, the nickel-cobalt dual-ligand metal organic framework material is a core-shell dual-layer structure, the core-shell dual-layer structure comprises a core and a shell, the core is a cobalt-based metal organic framework material, and the shell is a nickel-based organic framework material.
The invention also provides a preparation method of the nickel-cobalt double-ligand metal organic framework material, which comprises the following steps: (1) forming a cobalt-based metal organic framework material serving as an internal nuclear shell layer of the bimetallic organic framework material by taking a cobalt ion compound as a metal ion and a imidazole organic ligand as an organic ligand through coordination in a solvent; (2) selecting a solvent, preparing a seed solution containing nickel ions, and putting a cobalt-based metal organic framework material into the seed solution to obtain the cobalt-based metal organic framework material containing the nickel ion seed layer; (3) dissolving the cobalt-based metal organic framework material containing the nickel ion seed layer obtained in the step (2) and the organic ligand in dispersion liquid by using a toluene organic ligand as an organic ligand to form a mixed liquid, and pouring the mixed liquid into a reaction kettle for reaction to obtain a precursor of the nickel-cobalt double-ligand metal organic framework material; (4) and (4) heating the precursor of the nickel-cobalt dual-ligand metal-organic framework material obtained in the step (3) in a 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 0.025 mol/L-0.05 mol/L; the imidazole organic ligand is dissolved in anhydrous methanol, water or a mixture thereof, and the concentration range is 0.4 mol/L-0.8 mol/L. The imidazole organic ligand is one of dimethyl imidazole, ethoxy quinoline and benzimidazole or a mixture thereof. Slowly adding the dimethyl imidazole solution into a cobalt nitrate hexahydrate solution while keeping magnetic stirring, then stirring for 8-20 minutes while keeping the magnetic stirring at 300-450 r/min, sealing and standing for 15-25 hours; and centrifuging by using methanol/ethanol as a solvent, washing for 1-3 times, and finally drying for 5-15 hours at the temperature of 60-90 ℃.
Preferably, in the step (2), the solvent is one or a mixture of ethanol, methanol and deionized water, 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). And adding the cobalt-based MOF after a nickel chloride solution is formed, carrying out ultrasonic treatment for 10-30 minutes, and stirring for 10-30 minutes to obtain the cobalt-based MOF containing the nickel ion seed layer.
Preferably, in the step (3), the toluene organic ligand is one of mesitylene, trinitrotoluene, xylene or a mixture thereof. The molar ratio of the toluene organic ligand to the nickel compound is 1 (1-3). Taking the ionic water and the DMF as dispersion liquid, and stirring the dispersion liquid in a liner of a reaction kettle at a magnetic stirring speed of 300-500 r/min for 20-45 minutes; carrying out hydrothermal reaction in a blast oven at 100-170 ℃ for 9-14 hours; and during post-treatment, the centrifugal rotating speed is 5000-9000 r/min, the solvent used for centrifugation is ethanol/ionized water, washing is carried out for 1-3 times, and finally drying is carried out for 7-14 hours at the temperature of 60-90 ℃.
Preferably, the annealing process and conditions of the product obtained in the step (3) are that under the atmosphere of argon/nitrogen/argon-hydrogen mixed gas, the temperature is firstly increased to 500-800 ℃ at the speed of 2-10 ℃/min, the temperature is kept for 1-3 hours, and the carbonized MOF derivative is obtained after overnight cooling to room temperature.
The invention also provides an application of the nickel-cobalt double-ligand metal-organic framework material as an electromagnetic shielding material.
Preferably, the nickel-cobalt dual-ligand metal-organic framework material provided by the invention is applied as an electromagnetic shielding material, the nickel-cobalt dual-ligand metal-organic framework material is filled into resin or paraffin and is coated 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 dual-ligand metal-organic framework material accounts for 40-50% of the total weight of the coating.
The invention has the following beneficial effects:
(1) the method adopts a mode of designing a Metal Organic Framework (MOF) structure, designs MOF precursors with different morphologies by controlling the ratio of a second ligand to nickel, and then carbonizes the precursors in a reducing atmosphere to obtain the novel MOF derivative. Because of 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, such as the minimum reflection loss value and the bandwidth range, of the composite material is greatly enhanced compared with the traditional wave-absorbing filler with a single absorption mechanism;
(2) according to the invention, the morphology of the precursor MOF is controlled by adjusting the proportion of the double ions and the double ligands, and the precursor MOF can be converted from a sea urchin shape to a rod shape or a flower shape, so that the dielectric loss performance of the precursor MOF is adjusted to achieve the effect of adjusting the wave absorption performance.
Drawings
FIG. 1 is a diagram of a diionic, biligand MOF-1:1 prepared in example 2 of the present invention; magnification: 15000 times;
FIG. 2 is a diagram of a diionic, biligand MOF-1:1 prepared in example 2 of the present invention; magnification: 30000 times.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Cobalt nitrate hexahydrate is used as metal ions, dimethyl imidazole is used as an organic ligand, and 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 several hours and is used as an inner nuclear shell layer of double MOFs;
1.1488g of cobalt nitrate hexahydrate was added to 80ml of anhydrous methanol as a solution A (concentration: 0.05 mol/L); 5.1904g of dimethylimidazole was added to 80ml of anhydrous methanol as a B solution (concentration: 0.8 mol/L); slowly adding the dimethyl imidazole solution into the cobalt nitrate hexahydrate solution under the condition of keeping the magnetic stirring at 100r/min, then keeping the magnetic stirring at 360r/min for stirring for 12 minutes, centrifuging by using ethanol as a solvent, washing for 3 times, and finally drying for 12 hours at 60 ℃.
2) Preparing an ethanol seed solution containing nickel ions by using absolute ethanol as a solvent according to the mass ratio of the cobalt-based MOF to nickel chloride hexahydrate of 1:1, adding the cobalt-based MOF after a 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 containing the nickel ion seed layer.
Example 2
1) Cobalt chloride hexahydrate is used as metal ions, benzimidazole is used as an organic ligand, and 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 several hours and is used as an inner nuclear shell layer of double MOFs;
0.4759g of cobalt chloride hexahydrate was added to 60ml of anhydrous methanol as a solution A (concentration: 0.025 mol/L); 3.7390g of benzimidazole was added to 50ml of anhydrous methanol as a B solution (concentration: 0.4 mol/L); the solution of dimethyl imidazole was slowly added to the solution of cobalt nitrate hexahydrate while maintaining magnetic stirring, followed by stirring for 8 minutes while maintaining magnetic stirring at 300r/min, centrifugation using methanol as a solvent, and washing 3 times, and finally drying at 60 ℃ for 15 hours.
2) The method comprises the steps of taking deionized water as a solvent, preparing a seed solution containing nickel ions according to the mass ratio of cobalt-based MOF to nickel chloride hexahydrate of 2:1, adding cobalt-based MOF after a 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 containing a nickel ion seed layer.
3) Preparing 45ml of dispersion, filling into a 100ml reaction kettle liner, wherein the weight ratio of ethanol: deionized water: DMF 1:1: 1; adding the obtained cobalt-based MOF containing the nickel ion seed layer and 0.084g of mesitylene into the dispersion liquid, wherein the molar ratio of the mesitylene to nickel chloride hexahydrate is 1: 1; the magnetic stirring speed of the dispersion 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 ℃; and after the product is cooled, carrying out centrifugal treatment on the product, wherein the centrifugal rotation speed is 5000r/min, the solvent used for centrifugation is deionized water, washing for 2 times, and finally carrying out suction filtration on the product and drying for 14 hours at the temperature of 60 ℃. Thereby obtaining the sea urchin-shaped double-ion double-ligand MOF precursor.
4) And (3) preparing the carbonized MOF derivative, namely an annealing process and conditions, namely heating to 500 ℃ at a speed of 10 ℃/min in an argon/hydrogen mixed gas atmosphere, preserving heat for 1 hour, and cooling to room temperature overnight to obtain the carbonized MOF derivative.
5) Electromagnetic parameters of the nickel cobalt dual-ligand MOF derivative are tested in the range of 2-18 GHz, the prepared MOF derivative is firstly dispersed in a resin matrix, when the filling amount is 40%, the thickness of the material is 1.13mm, and the optimal reflection loss is-50.2 dB.
Example 3
1) Cobalt sulfate heptahydrate is used as metal ions, dimethyl imidazole is used as an organic ligand, and cobalt-based MOF is formed through coordination in a deionized water solvent, namely the cobalt-based MOF is obtained through magnetic stirring for a period of time and standing for several hours and 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 a solution A (concentration: 0.05 mol/L); 2.5952g of dimethylimidazole were added to 80ml of deionized water as a B solution (concentration: 0.4 mol/L); the dimethyl imidazole solution is slowly added into the cobalt nitrate hexahydrate solution under the condition of keeping the magnetic stirring, then the mixture is stirred for 12 minutes under the condition of keeping the magnetic stirring at 360r/min, the solvent used in the centrifugation is ethanol, the mixture is washed for 2 times, and finally the mixture is dried for 9 hours at 70 ℃.
2) Preparing an ethanol seed solution containing nickel ions by using absolute ethanol as a solvent according to the mass ratio of the cobalt-based MOF to nickel chloride hexahydrate of 1:1, adding the cobalt-based MOF after a 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 containing the nickel ion seed layer.
3) Preparing 60ml of dispersion, and filling the dispersion into a 100ml reaction kettle liner, wherein the weight ratio of ethanol: deionized water: DMF 1:1: 1; adding the obtained cobalt-based MOF containing the nickel ion seed layer and 0.037g of xylene into a dispersion liquid, wherein the molar ratio of the xylene to nickel chloride hexahydrate is 1: 2; the magnetic stirring speed of the dispersion 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, the centrifugal rotating speed is 8500r/min, the solvent used in the centrifugation is ethanol, the washing is carried out for 2 times, and finally, the product is subjected to suction filtration and is dried for 9 hours at the temperature of 70 ℃. Thereby obtaining the precursor of the rodlike double-ion double-ligand MOF with better dispersity.
4) And (3) preparing the carbonized MOF derivative, namely an annealing process and conditions, namely heating to 700 ℃ at a speed of 2 ℃/min in an argon atmosphere, preserving heat for 2 hours, and cooling to room temperature overnight to obtain the carbonized MOF derivative.
5) Electromagnetic parameters of the nickel-cobalt dual-ligand MOF derivative are tested in the range of 2-18 GHz, the prepared MOF derivative is firstly dispersed in a paraffin matrix, when the filling amount is 50%, the thickness of the material is 3.35mm, and the optimal reflection loss is-41.6 dB.
Example 4
1) Cobalt nitrate hexahydrate is used as metal ions, dimethyl imidazole is used as an organic ligand, and cobalt-based MOF is formed through coordination in a methanol solvent, namely the cobalt-based MOF is obtained through magnetic stirring and standing for several hours and is used as an inner nuclear shell layer of 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 anhydrous methanol as a B solution (concentration: 0.8 mol/L); under magnetic stirring, slowly adding the dimethyl imidazole solution into the cobalt nitrate hexahydrate solution, then stirring for 20 minutes under magnetic stirring at 450r/min, centrifuging, using ethanol and methanol as solvents, washing for 1 time respectively, and finally drying for 5 hours at 90 ℃.
2) Preparing a nickel ion-containing methanol seed solution by taking anhydrous methanol as a solvent according to the mass ratio of the cobalt-based MOF to nickel chloride hexahydrate of 1:2, adding the cobalt-based MOF after a 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 nickel ion-containing cobalt-based MOF of the nickel ion seed layer.
3) 75ml of dispersion was prepared and charged into a 100ml reactor liner, wherein ethanol: deionized water: DMF 1:1: 1; adding the obtained cobalt-based MOF containing the nickel ion seed layer and 0.053g of trinitrotoluene into a dispersion liquid, wherein the molar ratio of the trinitrotoluene to nickel chloride hexahydrate is 1: 3; the magnetic stirring speed of the dispersion 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 centrifuged at 9000r/min, ethanol and deionized water are used as solvents for centrifugation, the solvents are respectively washed for 1 time, and finally the product is filtered and dried for 7 hours at 90 ℃. Thereby obtaining petal-shaped and part rod-shaped dual-ion dual-ligand MOF precursors.
4) And (3) preparing the carbonized MOF derivative, namely an annealing process and conditions, namely heating to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature overnight to obtain the carbonized MOF derivative.
5) Electromagnetic parameters of the nickel cobalt dual-ligand MOF derivative are tested in the range of 2-18 GHz, the prepared MOF derivative is firstly dispersed in a resin matrix, when the filling amount is 40%, the thickness of the material is 1.59mm, and the optimal reflection loss is-55.6 dB.
Comparative example
1) Cobalt nitrate hexahydrate is used as metal ions, dimethyl imidazole is used as an organic ligand, and 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 several hours and is used as an inner nuclear shell layer of double MOFs;
1.1488g of cobalt nitrate hexahydrate is added into 80ml of anhydrous methanol to serve as a solution A; 2.5952g of dimethylimidazole was added to 80ml of anhydrous methanol as a B solution; slowly adding the dimethyl imidazole solution into the cobalt nitrate hexahydrate solution under the condition of keeping the magnetic stirring at 100r/min, then keeping the magnetic stirring at 360r/min for stirring for 12 minutes, centrifuging by using ethanol as a solvent, washing for 3 times, and finally drying for 12 hours at 60 ℃.
2) And (3) preparing the carbonized MOF derivative, namely an annealing process and conditions, namely heating to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature overnight to obtain the carbonized MOF derivative.
3) Electromagnetic parameters of the nickel-cobalt dual-ligand MOF derivative are tested in the range of 2-18 GHz, the prepared MOF derivative is firstly dispersed in a paraffin matrix, when the filling amount is 40%, the thickness of the material is 3.15mm, and the optimal reflection loss is only-10.3 dB.
However, the above description is only exemplary of the present invention, and the scope of the present invention should not be limited thereby, and the replacement of the equivalent components or the equivalent changes and modifications made according to the protection scope of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The nickel-cobalt dual-ligand metal-organic framework material is characterized by being of a core-shell dual-layer structure, wherein the core-shell dual-layer structure comprises an inner core and an outer shell, the inner core is made of a cobalt-based metal-organic framework material, and the outer shell is made of a nickel-based organic framework material.
2. The method of preparing a nickel cobalt dual ligand metal organic framework material of claim 1 comprising the steps of:
(1) forming a cobalt-based metal organic framework material serving as an internal nuclear shell layer of the bimetallic organic framework material by taking a cobalt ion compound as a metal ion and a imidazole organic ligand as an organic ligand through coordination in a solvent;
(2) selecting a solvent, preparing a seed solution containing nickel ions, and putting a cobalt-based metal organic framework material into the seed solution to obtain the cobalt-based metal organic framework material containing the nickel ion seed layer;
(3) dissolving the cobalt-based metal organic framework material containing the nickel ion seed layer obtained in the step (2) and the organic ligand in dispersion liquid by using a toluene organic ligand as an organic ligand to form a mixed liquid, and pouring the mixed liquid into a reaction kettle for reaction to obtain a precursor of the nickel-cobalt double-ligand metal organic framework material;
(4) and (4) heating the precursor of the nickel-cobalt dual-ligand metal-organic framework material obtained in the step (3) in a mixed gas atmosphere, and cooling to room temperature to obtain the nickel-cobalt dual-ligand metal-organic framework material.
3. The method for preparing a nickel-cobalt dual-ligand metal-organic framework material according to claim 2, wherein the cobalt ion compound in step (1) is one of cobalt nitrate hexahydrate, cobalt sulfate heptahydrate, cobalt chloride hexahydrate or a mixture thereof.
4. The method for preparing a nickel-cobalt dual-ligand metal-organic framework material according to claim 3, which comprises the steps of (1), dissolving the cobalt ion compound in absolute methanol, water or a mixture thereof to obtain a concentration ranging from 0.025mol/L to 0.05 mol/L; the imidazole organic ligand is dissolved in anhydrous methanol, water or a mixture thereof, and the concentration range is 0.4 mol/L-0.8 mol/L.
5. The method for preparing the nickel-cobalt dual-ligand metal-organic framework material according to claim 2, wherein the imidazole-based organic ligand in the step (1) is one of dimethyl imidazole, ethoxy quinoline and benzimidazole or a mixture thereof.
6. The method for preparing the nickel-cobalt dual-ligand metal-organic framework material according to claim 3, 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).
7. The method for preparing the nickel-cobalt dual-ligand metal-organic framework material according to claim 3, wherein the toluene organic ligand in the step (3) is one of mesitylene, trinitrotoluene, xylene or a mixture thereof.
8. The preparation method of the nickel-cobalt dual-ligand metal-organic framework material according to claim 3, wherein the molar ratio of the toluene organic ligand to the nickel compound in the step (3) is 1 (1-3).
9. Use of the nickel cobalt dual ligand metal organic framework material of claim 1 as an electromagnetic wave absorbing material.
10. The use of the Ni-Co dual-ligand metal-organic framework material as an electromagnetic wave absorbing material according to claim 9, wherein the Ni-Co dual-ligand metal-organic framework material is filled in resin or paraffin wax and coated on the surface of an object to form a coating, the thickness of the coating is 1.13-3.35 mm, and the Ni-Co dual-ligand metal-organic framework material accounts for 40-50% of the total weight of the coating.
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