CN113801631B - MnCo 2 O 4 ZIF-67/Ni wave-absorbing material and preparation method thereof - Google Patents
MnCo 2 O 4 ZIF-67/Ni wave-absorbing material and preparation method thereof Download PDFInfo
- Publication number
- CN113801631B CN113801631B CN202111317691.4A CN202111317691A CN113801631B CN 113801631 B CN113801631 B CN 113801631B CN 202111317691 A CN202111317691 A CN 202111317691A CN 113801631 B CN113801631 B CN 113801631B
- Authority
- CN
- China
- Prior art keywords
- zif
- mnco
- mixed solution
- wave
- absorbing material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011358 absorbing material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011259 mixed solution Substances 0.000 claims abstract description 66
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 44
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 43
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 14
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 14
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 14
- 239000011565 manganese chloride Substances 0.000 claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- 239000013049 sediment Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002070 nanowire Substances 0.000 claims description 5
- 230000003628 erosive effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000012621 metal-organic framework Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 1
- 241000656145 Thyrsites atun Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material comprises the following steps: dissolving manganese chloride, cobalt nitrate, urea and ammonium fluoride in a mixed solution of deionized water and ethanol, transferring the mixed solution into an autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, centrifuging after the reaction is finished, washing, and drying to obtain a precursor product; annealing the precursor product in air to obtain manganese cobaltate; compounding manganese cobaltate with Zif-67, and doping Ni to obtain MnCo 2 O 4 ZIF-67/Ni wave-absorbing material. The preparation method has the advantages of simple process, low cost, short time consumption and controllable conditions, does not need any surfactant or organic template agent in the synthesis process, adopts nontoxic raw materials, meets the industrial production direction of environmental protection requirements in the raw materials and the preparation process, lays a good foundation for application research, and has good prospect in the wave absorbing field.
Description
Technical Field
The invention relates to a wave-absorbing material technology, in particular to a MnCo 2 O 4 An @ ZIF-67/Ni wave-absorbing material and a preparation method thereof.
Background
With the rapid development of wireless electronic technology, wireless electronic technology and artificial intelligence have brought convenience and intelligent life to humans. However, the electromagnetic interference problem is increasing, which seriously jeopardizes the health of people and the normal use of electronic equipment. Electromagnetic interference is the fourth largest source of environmental pollution following the industrial "three wastes", and therefore, the manufacture of highly efficient electromagnetic absorbing materials that interact with electromagnetic waves and convert electromagnetic wave energy into heat energy or other forms of energy is a critical solution.
Among the wave-absorbing materials, ferrite has many good applications in the military and civil fields due to its high saturation magnetization, peroxide resistance and corrosion resistance. However, due to the limitation of the "Snoek" limit, the magnetic loss in the high frequency region is small, and electromagnetic waves cannot be effectively absorbed. Therefore, it is of great importance to explore new microwave adsorbents that replace traditional ferrite materials. Due to its broad magnetic, optical and electronic properties, some transition metal oxides (including manganese, cobalt and nickel oxides) have been widely used in the fields of high density magnetic storage, magnetic resonance imaging, catalysis, sensors, electronics. MnCo 2 O 4 Nanomaterial has been widely studied as a battery or a capacity device, but studies as a wave-absorbing material have been recently reported.
Metal Organic Frameworks (MOFs) are a versatile and structurally programmable nanoporous material that is a precursor for the preparation of porous carbon and carbon-based composites. Various MOFs, such as MOF-5, ZIF67, ZIF-8 and Al-PCP, are used in the synthesis of atomic doped porous carbon and in the fields of energy storage, gas absorption, catalysis, electromagnetic wave absorption, and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the MnCo with simple preparation process, low cost and wave absorbing performance 2 O 4 An @ ZIF-67/Ni wave-absorbing material and a preparation method thereof.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material comprises the following steps:
(1) Manganese chloride, cobalt nitrate, urea and ammonium fluoride are mixed according to the mole ratio of 1: (2-3): (2.5-3.5): (0.5-3) are dissolved in deionized water and ethanol in sequence, and the volume ratio of the deionized water to the ethanol is (3-5): 1, obtaining a mixed solution A;
(2) Transferring the mixed solution A into an autoclave with a polytetrafluoroethylene lining, performing airtight reaction for 11-13h at 110-130 ℃, cooling to room temperature after the reaction is finished, centrifuging to obtain black sediment, washing with deionized water and ethanol successively, and drying to obtain a precursor product;
(3) Annealing the precursor product in air to obtain manganese cobaltate;
(4) Preparing cobalt nitrate solution with the concentration of 0.03-0.05mol/L and dimethyl imidazole solution with the concentration of 0.1-0.2mol/L by taking methanol as a solvent respectively; then the mass ratio of manganese cobaltate to cobalt nitrate is (12-17): adding manganese cobaltate into a cobalt nitrate solution, stirring and dissolving to obtain a mixed solution B; the molar ratio of cobalt nitrate to dimethyl imidazole is 1: (2-4) mixing the mixed solution B with the dimethyl imidazole solution, stirring for 35-45min to fully and uniformly mix the mixed solution B, standing the mixed solution B for reaction for 22-25h, centrifugally separating the mixed solution B to obtain sediment, fully washing the sediment with deionized water and ethanol, and drying the sediment to obtain MnCo 2 O 4 A @ ZIF-67 complex;
(5) MnCo is mixed with 2 O 4 The weight ratio of the @ ZIF-67 compound to the nickel nitrate is 1: (1-2) sequentially dissolving in ethanol to obtain a mixed solution C, standing for reaction for 22-25h, centrifuging to obtain a sediment, washing with deionized water and ethanol sequentially, drying, and annealing at 400-650 ℃ for 1.75-2.25h under the protection of argon to obtain MnCo 2 O 4 ZIF-67/Ni wave-absorbing material.
Further, the concentration of the manganese chloride in the mixed solution A in the step (1) is 0.01-0.03mol/L.
Further, the drying temperature in the steps (2), (4) and (5) is 60-80 ℃ and the drying time is 10-15h.
Further, the annealing temperature in the step (3) is 350-400 ℃ and the annealing time is 1.75-2.25h.
Further, mnCo in the mixed solution C in the step (5) 2 O 4 ZIF-67 compositeThe concentration of the product is 2-3g/L.
The invention also relates to the MnCo prepared by the method 2 O 4 @ZIF-67/Ni wave-absorbing material, the MnCo 2 O 4 The microstructure of the @ ZIF-67/Ni wave absorbing material is a flower-sphere structure consisting of eroding rock-like nanowires.
Compared with the prior art, the invention has the following technical effects:
1. constructing a variety of hetero interfaces with materials having a variety of complementary or reinforcing properties is critical to solving the electromagnetic wave absorption problem, and the present application uses the synergistic effect of manganese cobaltate with a metal-organic framework (zif 67) having a unique structure and nickel to enhance conductivity loss, strong dipole polarization and multi-interface polarization, and has optimal impedance matching properties.
2. In the application, coO@N/C polyhedrons formed by the Zif67 through the annealing conversion of the step 5 are embedded into manganese cobaltate to form a nano porous structure, so that electromagnetic waves are promoted to be scattered between composite materials for multiple times; in addition, the final synthesized MnCo 2 O 4 The @ ZIF-67/Ni wave-absorbing material can form the following interfaces: the outer layer is a hetero-interface formed by CoO@N/C formed by Zif67 conversion and manganese cobaltate, and a hetero-interface formed by Co and Mn, n-doped graphitized carbon can form stronger interfacial relaxation polarization to dissipate electromagnetic wave energy, and the interface between C/C, C/air and C/Ni induces a large amount of interfacial polarization. Meanwhile, under the action of an alternating electric field, defects in manganese cobaltate and dipoles in n-doped disordered carbon derived from ZIF67 cause defect polarization and dipole polarization, and the like, which increase dielectric loss and thus electromagnetic wave adsorption performance. Thus, the MnCo prepared by the present invention 2 O 4 The @ ZIF-67/Ni wave absorbing material can effectively eliminate incident electromagnetic waves.
3. The preparation method has the advantages of simple process, low cost, short time consumption and controllable conditions, does not need any surfactant or organic template agent in the synthesis process, adopts nontoxic raw materials, meets the industrial production direction of environmental protection requirements in the raw materials and the preparation process, lays a good foundation for application research, and has good prospect in the wave absorbing field.
Drawings
FIG. 1 shows MnCo according to example 4 of the present invention 2 O 4 SEM image of the @ ZIF-67/Ni wave-absorbing material before annealing under the protection of argon;
FIG. 2 shows MnCo prepared in example 4 of the present invention 2 O 4 SEM image of ZIF-67/Ni wave-absorbing material.
Detailed Description
The following examples illustrate the invention in further detail.
The present embodiment provides a MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material comprises the following steps:
(1) Manganese chloride, cobalt nitrate, urea and ammonium fluoride are mixed according to the mole ratio of 1: (2-3): (2.5-3.5): (0.5-3) are dissolved in deionized water and ethanol in sequence, and the volume ratio of the deionized water to the ethanol is (3-5): 1, obtaining a mixed solution A;
(2) Transferring the mixed solution A into an autoclave with a polytetrafluoroethylene lining, performing airtight reaction for 11-13h at 110-130 ℃, cooling to room temperature after the reaction is finished, centrifuging to obtain black sediment, washing with deionized water and ethanol successively, and drying to obtain a precursor product;
(3) Annealing the precursor product in air to obtain manganese cobaltate;
(4) Preparing cobalt nitrate solution with the concentration of 0.03-0.05mol/L and dimethyl imidazole solution with the concentration of 0.1-0.2mol/L by taking methanol as a solvent respectively; then the mass ratio of manganese cobaltate to cobalt nitrate is (12-17): adding manganese cobaltate into a cobalt nitrate solution, stirring and dissolving to obtain a mixed solution B; the molar ratio of cobalt nitrate to dimethyl imidazole is 1: (2-4) mixing the mixed solution B with the dimethyl imidazole solution, stirring for 35-45min to fully and uniformly mix the mixed solution B, standing the mixed solution B for reaction for 22-25h, centrifugally separating the mixed solution B to obtain sediment, fully washing the sediment with deionized water and ethanol, and drying the sediment to obtain MnCo 2 O 4 A @ ZIF-67 complex;
(5) MnCo is mixed with 2 O 4 The weight ratio of the @ ZIF-67 compound to the nickel nitrate is 1: (1-2) sequentially dissolving in ethanol to obtain a mixed solution C, standing for 22-25h, centrifuging to obtain a sediment, sequentially adding deionized water and ethanolWashing, drying, and annealing at 400-650deg.C under argon for 1.75-2.25 hr to obtain MnCo 2 O 4 ZIF-67/Ni wave-absorbing material.
This example also relates to MnCo prepared by the above method 2 O 4 @ZIF-67/Ni wave-absorbing material, the MnCo 2 O 4 The microstructure of the @ ZIF-67/Ni wave absorbing material is a flower-sphere structure consisting of eroding rock-like nanowires.
In order to further describe the technical scheme of the present invention in detail, the following description is made with reference to specific embodiments.
Example 1
The present embodiment provides a MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material comprises the following steps:
(1) Manganese chloride, cobalt nitrate, urea and ammonium fluoride are mixed according to the mole ratio of 1:2:2.5:0.5 is dissolved in deionized water and ethanol in sequence by ultrasonic or stirring, and the volume ratio is 3:1 to obtain a mixed solution A with the manganese chloride concentration of 0.01 mol/L;
(2) Transferring the mixed solution A into an autoclave with a polytetrafluoroethylene lining, performing airtight reaction at 110 ℃ for 13 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain black sediment, washing with deionized water for several times, fully washing with ethanol, and drying at 60 ℃ for 15 hours to obtain a precursor product;
(3) Annealing the precursor product for 1.75 hours at 400 ℃ in an air atmosphere to obtain manganese cobaltate;
(4) Preparing a cobalt nitrate solution with the concentration of 0.03mol/L and a dimethyl imidazole solution with the concentration of 0.1mol/L by taking methanol as a solvent respectively; then the mass ratio of manganese cobaltate to cobalt nitrate is 15: adding manganese cobaltate into a cobalt nitrate solution, stirring for 15min to fully dissolve and uniformly mix the manganese cobaltate and the cobalt nitrate solution to obtain a mixed solution B; the molar ratio of cobalt nitrate to dimethyl imidazole is 1:2, mixing the mixed solution B with a dimethyl imidazole solution, stirring for 35min to fully and uniformly mix the mixed solution B, standing the mixed solution B for reaction for 22h, centrifugally separating the mixed solution B to obtain a sediment, sequentially washing the sediment with deionized water and ethanol, and drying the sediment at 80 ℃ for 10h to obtain a compound of manganese cobaltate and Zif-67;
(5) Cobalt is mixed withThe mass ratio of the manganese acid to the Zif-67 compound to the nickel nitrate is 1:1 are dissolved in ethanol successively to obtain a mixed solution C with the concentration of a compound of manganese cobaltate and Zif-67 of 2g/L, the mixed solution C is stirred magnetically for 35min to fully and uniformly mix, then the mixed solution C is stood for reaction for 22h, the deposited material is obtained by centrifugation, and is fully washed by ionized water and ethanol in sequence, and then the obtained product is dried at 60 ℃ for 15h and annealed at 600 ℃ for 1.75h under the protection of argon gas to obtain MnCo 2 O 4 ZIF-67/Ni wave-absorbing material.
Example 2
The present embodiment provides a MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material comprises the following steps:
(1) Manganese chloride, cobalt nitrate, urea and ammonium fluoride are mixed according to the mole ratio of 1:2.5:3:2 are dissolved in deionized water and ethanol in sequence by ultrasonic or stirring according to the volume ratio of 4:1 to obtain a mixed solution A with the manganese chloride concentration of 0.02 mol/L;
(2) Transferring the mixed solution A into an autoclave with a polytetrafluoroethylene lining, performing airtight reaction at 120 ℃ for 12 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain black sediment, washing with deionized water for several times, fully washing with ethanol, and drying at 80 ℃ for 10 hours to obtain a precursor product;
(3) Annealing the precursor product for 2.25 hours at 350 ℃ in an air atmosphere to obtain manganese cobaltate;
(4) Preparing cobalt nitrate solution with the concentration of 0.04mol/L and dimethyl imidazole solution with the concentration of 0.15mol/L by taking methanol as a solvent respectively; then the mass ratio of manganese cobaltate to cobalt nitrate is 12: adding manganese cobaltate into a cobalt nitrate solution, stirring for 25min to fully dissolve and uniformly mix the manganese cobaltate and the cobalt nitrate solution to obtain a mixed solution B; the molar ratio of cobalt nitrate to dimethyl imidazole is 1:3, mixing the mixed solution B with a dimethyl imidazole solution, stirring for 45min to fully and uniformly mix the mixed solution B, standing the mixed solution B for reaction for 24h, centrifugally separating the mixed solution B to obtain a sediment, fully washing the sediment by deionized water and ethanol, and drying the sediment at 60 ℃ for 15h to obtain a compound of manganese cobaltate and Zif-67;
(5) The composite of manganese cobaltate and Zif-67 and nickel nitrate are mixed according to the mass ratio of 1:2 are dissolved in ethanol in sequence to obtain the compound with the concentration of 3 of manganese cobaltate and Zif-67g/L mixed solution C is stirred magnetically for 45min to fully and uniformly mix, then is kept stand for reaction for 24h, is centrifuged to obtain sediment, is washed fully by ionized water and ethanol successively, is dried at 80 ℃ for 10h and is annealed at 400 ℃ for 2.25h under the protection of argon to obtain MnCo 2 O 4 ZIF-67/Ni wave-absorbing material.
Example 3
The present embodiment provides a MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material comprises the following steps:
(1) Manganese chloride, cobalt nitrate, urea and ammonium fluoride are mixed according to the mole ratio of 1:3:3.5: and 3, dissolving in deionized water and ethanol successively by ultrasonic or stirring according to the volume ratio of 5:1 to obtain a mixed solution A with the manganese chloride concentration of 0.03 mol/L;
(2) Transferring the mixed solution A into an autoclave with a polytetrafluoroethylene lining, performing airtight reaction at 130 ℃ for 11 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain black sediment, washing with deionized water for several times, fully washing with ethanol, and drying at 70 ℃ for 12 hours to obtain a precursor product;
(3) Annealing the precursor product for 2 hours at 380 ℃ in an air atmosphere to obtain manganese cobaltate;
(4) Preparing a cobalt nitrate solution with the concentration of 0.05mol/L and a dimethyl imidazole solution with the concentration of 0.2mol/L by taking methanol as a solvent respectively; then the mass ratio of manganese cobaltate to cobalt nitrate is 17: adding manganese cobaltate into a cobalt nitrate solution, stirring for 20min to fully dissolve and uniformly mix the manganese cobaltate and the cobalt nitrate solution to obtain a mixed solution B; the molar ratio of cobalt nitrate to dimethyl imidazole is 1:4, mixing the mixed solution B with a dimethyl imidazole solution, stirring for 40min to fully and uniformly mix the mixed solution B, standing the mixed solution B for reaction for 25h, centrifugally separating the mixed solution B to obtain a sediment, fully washing the sediment by deionized water and ethanol, and drying the sediment at 70 ℃ for 12h to obtain a compound of manganese cobaltate and Zif-67;
(5) The composite of manganese cobaltate and Zif-67 and nickel nitrate are mixed according to the mass ratio of 1:1.5 dissolving in ethanol successively to obtain a mixed solution C with a compound concentration of manganese cobaltate and Zif-67 of 2.5g/L, magnetically stirring for 40min to fully mix, standing for reaction for 25h, centrifuging to obtain a sediment, and sequentially adding ionized water and ethanolWashing with alcohol, drying at 70deg.C for 12 hr, and annealing at 550deg.C under argon protection for 2 hr to obtain MnCo 2 O 4 ZIF-67/Ni wave-absorbing material.
Example 4
The present embodiment provides a MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material comprises the following steps:
(1) Manganese chloride, cobalt nitrate, urea and ammonium fluoride are mixed according to the mole ratio of 1:2:3: and 3, dissolving in deionized water and ethanol successively by ultrasonic or stirring according to the volume ratio of 4:1 to obtain a mixed solution A with the manganese chloride concentration of 0.015 mol/L;
(2) Transferring the mixed solution A into an autoclave with a polytetrafluoroethylene lining, performing airtight reaction at 120 ℃ for 12 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain black sediment, washing with deionized water for several times, fully washing with ethanol, and drying at 65 ℃ for 15 hours to obtain a precursor product;
(3) Annealing the precursor product for 2 hours at 400 ℃ in an air atmosphere to obtain manganese cobaltate;
(4) Preparing cobalt nitrate solution with the concentration of 0.04mol/L and dimethyl imidazole solution with the concentration of 0.16mol/L by taking methanol as a solvent respectively; then the mass ratio of manganese cobaltate to cobalt nitrate is 14: adding manganese cobaltate into a cobalt nitrate solution, stirring for 20min to fully dissolve and uniformly mix the manganese cobaltate and the cobalt nitrate solution to obtain a mixed solution B; the molar ratio of cobalt nitrate to dimethyl imidazole is 1:3.5 mixing the mixed solution B with the dimethyl imidazole solution, stirring for 40min to fully and uniformly mix the mixed solution B, standing the mixed solution B for reaction for 25h, centrifugally separating the mixed solution B to obtain a sediment, washing the sediment with deionized water and ethanol successively, and drying the sediment at 65 ℃ for 15h to obtain a compound of manganese cobaltate and Zif-67;
(5) The composite of manganese cobaltate and Zif-67 and nickel nitrate are mixed according to the mass ratio of 1:2 are dissolved in ethanol successively to obtain a mixed solution C with the concentration of a compound of manganese cobaltate and Zif-67 of 2.5g/L, the mixed solution C is stirred magnetically for 40min to fully and uniformly mix, then the mixed solution C is stood for reaction for 23h, the precipitate is obtained by centrifugation, and is fully washed by ionized water and ethanol successively, and then the MnCo is obtained after drying for 15h under the protection of argon and annealing for 2h under the 650 DEG C 2 O 4 ZIF-67/Ni absorberWave material.
FIGS. 1 and 2 are respectively a MnCo prepared in this example 2 O 4 SEM images of the ZIF-67/Ni wave-absorbing material before and after annealing under the protection of argon, and the microstructure before argon annealing is a flower-sphere structure consisting of a dodecahedral metal-organic framework (MOF) and lamellar attached nanowires; after argon annealing, the dodecahedron Metal Organic Framework (MOF) and the lamellar attachments are destroyed in the pyrolysis process, and the nanowires of the original flower-ball structure are converted into uneven erosion rock. From the above results, it can be seen that the morphology of the composite material is changed substantially before and after annealing.
Claims (6)
1. MnCo 2 O 4 The preparation method of the @ ZIF-67/Ni wave-absorbing material is characterized by comprising the following steps:
(1) Manganese chloride, cobalt nitrate, urea and ammonium fluoride are mixed according to the mole ratio of 1: (2-3): (2.5-3.5): (0.5-3) are dissolved in deionized water and ethanol in sequence, and the volume ratio of the deionized water to the ethanol is (3-5): 1, obtaining a mixed solution A;
(2) Transferring the mixed solution A into an autoclave with a polytetrafluoroethylene lining, performing airtight reaction for 11-13h at 110-130 ℃, cooling to room temperature after the reaction is finished, centrifuging to obtain black sediment, washing with deionized water and ethanol successively, and drying to obtain a precursor product;
(3) Annealing the precursor product in air to obtain manganese cobaltate;
(4) Preparing cobalt nitrate solution with the concentration of 0.03-0.05mol/L and dimethyl imidazole solution with the concentration of 0.1-0.2mol/L by taking methanol as a solvent respectively; then the mass ratio of manganese cobaltate to cobalt nitrate is (12-17): adding manganese cobaltate into a cobalt nitrate solution, stirring and dissolving to obtain a mixed solution B; the molar ratio of cobalt nitrate to dimethyl imidazole is 1: (2-4) mixing the mixed solution B with the dimethyl imidazole solution, stirring for 35-45min to fully and uniformly mix the mixed solution B, standing the mixed solution B for reaction for 22-25h, centrifugally separating the mixed solution B to obtain sediment, fully washing the sediment with deionized water and ethanol, and drying the sediment to obtain MnCo 2 O 4 A @ ZIF-67 complex;
(5) MnCo is mixed with 2 O 4 The weight ratio of the @ ZIF-67 compound to the nickel nitrate is 1: (1-2) sequentially dissolving in ethanol to obtain a mixed solution C, standing for reaction for 22-25h, centrifuging to obtain a sediment, washing with deionized water and ethanol sequentially, drying, and annealing at 400-650 ℃ for 1.75-2.25h under the protection of argon to obtain MnCo 2 O 4 ZIF-67/Ni wave-absorbing material.
2. MnCo according to claim 1 2 O 4 The preparation method of the ZIF-67/Ni wave-absorbing material is characterized in that the concentration of manganese chloride in the mixed solution A in the step (1) is 0.01-0.03mol/L.
3. MnCo according to claim 1 2 O 4 The preparation method of the ZIF-67/Ni wave-absorbing material is characterized in that the drying temperature in the steps (2), (4) and (5) is 60-80 ℃ and the drying time is 10-15h.
4. MnCo according to claim 1 2 O 4 The preparation method of the ZIF-67/Ni wave-absorbing material is characterized in that the annealing temperature in the step (3) is 350-400 ℃ and the annealing time is 1.75-2.25h.
5. MnCo according to claim 1 2 O 4 A preparation method of the @ ZIF-67/Ni wave-absorbing material is characterized in that MnCo in the mixed solution C in the step (5) 2 O 4 The concentration of the @ ZIF-67 complex is 2-3g/L.
6. A MnCo prepared by the method of any one of claims 1-5 2 O 4 The @ ZIF-67/Ni wave absorbing material is characterized in that the MnCo 2 O 4 The microstructure of the @ ZIF-67/Ni wave absorbing material is a flower-sphere structure consisting of eroding rock-like nanowires.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111317691.4A CN113801631B (en) | 2021-11-09 | 2021-11-09 | MnCo 2 O 4 ZIF-67/Ni wave-absorbing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111317691.4A CN113801631B (en) | 2021-11-09 | 2021-11-09 | MnCo 2 O 4 ZIF-67/Ni wave-absorbing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113801631A CN113801631A (en) | 2021-12-17 |
| CN113801631B true CN113801631B (en) | 2024-02-02 |
Family
ID=78898531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111317691.4A Active CN113801631B (en) | 2021-11-09 | 2021-11-09 | MnCo 2 O 4 ZIF-67/Ni wave-absorbing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113801631B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114261950B (en) * | 2021-12-20 | 2024-03-29 | 徐州工程学院 | Tubular cobalt hybridization g-C 3 N 4 Material, microwave synthesis method thereof and application thereof in field of super capacitor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090071311A (en) * | 2007-12-27 | 2009-07-01 | 황민선 | Electric wave absorbent material, electric wave absorbent product containing the same and method for manufacturing the same |
| CN105885784A (en) * | 2016-04-18 | 2016-08-24 | 青岛大学 | Preparation method of wave-absorbing material adopting core-shell structure |
| CN109181640A (en) * | 2018-09-18 | 2019-01-11 | 北京科技大学 | The preparation method for the porous carbon absorbing material that cobalt and oxide are inlayed |
| CN109786766A (en) * | 2018-12-27 | 2019-05-21 | 上海理工大学 | A kind of preparation method of porous carbon carrying transition metal oxide composite |
| CN109911944A (en) * | 2019-03-08 | 2019-06-21 | 盱眙新远光学科技有限公司 | A kind of polyhedron MnCo2O4.5The preparation method of composite oxide material |
| CN111001821A (en) * | 2019-12-21 | 2020-04-14 | 哈尔滨工业大学 | Metal organic framework derived Co/C nanoparticle coated carbonized cotton fiber wave-absorbing material and preparation method thereof |
| CN111269694A (en) * | 2019-12-16 | 2020-06-12 | 南京工业大学 | Magnetoelectric composite nano porous wave-absorbing material and preparation method thereof |
| CN113292068A (en) * | 2021-06-24 | 2021-08-24 | 合肥工业大学 | Nickel-doped metal organic framework derived cobalt-carbon composite wave-absorbing material and preparation method thereof |
| CN113328262A (en) * | 2021-05-31 | 2021-08-31 | 青岛科技大学 | Preparation method of manganese oxide @ Ni-Co/graphite carbon nanocomposite |
-
2021
- 2021-11-09 CN CN202111317691.4A patent/CN113801631B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090071311A (en) * | 2007-12-27 | 2009-07-01 | 황민선 | Electric wave absorbent material, electric wave absorbent product containing the same and method for manufacturing the same |
| CN105885784A (en) * | 2016-04-18 | 2016-08-24 | 青岛大学 | Preparation method of wave-absorbing material adopting core-shell structure |
| CN109181640A (en) * | 2018-09-18 | 2019-01-11 | 北京科技大学 | The preparation method for the porous carbon absorbing material that cobalt and oxide are inlayed |
| CN109786766A (en) * | 2018-12-27 | 2019-05-21 | 上海理工大学 | A kind of preparation method of porous carbon carrying transition metal oxide composite |
| CN109911944A (en) * | 2019-03-08 | 2019-06-21 | 盱眙新远光学科技有限公司 | A kind of polyhedron MnCo2O4.5The preparation method of composite oxide material |
| CN111269694A (en) * | 2019-12-16 | 2020-06-12 | 南京工业大学 | Magnetoelectric composite nano porous wave-absorbing material and preparation method thereof |
| CN111001821A (en) * | 2019-12-21 | 2020-04-14 | 哈尔滨工业大学 | Metal organic framework derived Co/C nanoparticle coated carbonized cotton fiber wave-absorbing material and preparation method thereof |
| CN113328262A (en) * | 2021-05-31 | 2021-08-31 | 青岛科技大学 | Preparation method of manganese oxide @ Ni-Co/graphite carbon nanocomposite |
| CN113292068A (en) * | 2021-06-24 | 2021-08-24 | 合肥工业大学 | Nickel-doped metal organic framework derived cobalt-carbon composite wave-absorbing material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| MOF类衍生材料在电磁吸波领域的研究进展;张晓东;贺亦凡;刘思;闫婧;黄英;;材料开发与应用(第03期);第86-96页 * |
| Two-Step Solvothermal Synthesis of (Zn0.5Co0.5Fe2O4/Mn0.5Ni0.5Fe2O4)@C-MWCNTs Hybrid with Enhanced Low Frequency Microwave Absorbing Performance;Yin, Pengfei et al.;《NANOMATERIALS》;第9卷(第11期);第1601页 * |
| 尖晶石型纳米铁氧体的制备与吸波性能;邱琴;张晏清;张雄;;材料科学与工程学报;第27卷(第05期);第713-715+700页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113801631A (en) | 2021-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Design of morphology-controlled and excellent electromagnetic wave absorption performance of sheet-shaped ZnCo2O4 with a special arrangement | |
| Yuan et al. | Metal organic framework (MOF)-derived carbonaceous Co3O4/Co microframes anchored on RGO with enhanced electromagnetic wave absorption performances | |
| Wang et al. | A novel MOF-drived self-decomposition strategy for CoO@ N/C-Co/Ni-NiCo2O4 multi-heterostructure composite as high-performance electromagnetic wave absorbing materials | |
| Dai et al. | Fabrication of one-dimensional M (Co, Ni)@ polyaniline nanochains with adjustable thickness for excellent microwave absorption properties | |
| Chen et al. | Facile synthesis RGO/MnOx composite aerogel as high-efficient electromagnetic wave absorbents | |
| Yang et al. | Efficient electromagnetic wave absorption by SiC/Ni/NiO/C nanocomposites | |
| CN111675208B (en) | Sulfur-nitrogen doped hollow carbon nanotube composite material and preparation method and application thereof | |
| CN109054742B (en) | Fe-Co-RGO composite wave-absorbing material and preparation method thereof | |
| CN108520945B (en) | Nanotube array/carbon cloth composite material, flexible electrode, lithium ion battery and preparation method thereof | |
| CN105219345A (en) | A kind of preparation method of Z 250 iron nucleocapsid structure-Graphene composite wave-suction material | |
| CN108452813B (en) | MoS2/SrFe12O19Preparation method of composite magnetic photocatalyst | |
| CN107134575B (en) | Preparation method of sodium ion battery negative electrode material | |
| CN113801631B (en) | MnCo 2 O 4 ZIF-67/Ni wave-absorbing material and preparation method thereof | |
| CN115491177A (en) | MOF-derived carbon-based magnetic nanocomposite electromagnetic wave absorption material and preparation method thereof | |
| CN115915738A (en) | HOF-derived one-dimensional Ni-doped magnetic carbon-based nano composite material and preparation method thereof | |
| Swapnalin et al. | Multilayer intercalation: MXene/cobalt ferrite electromagnetic wave absorbing two-dimensional materials | |
| CN108711517B (en) | A kind of γ-Fe2O3Nano material and its preparation method and application | |
| CN111924864A (en) | MnO/MgO composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN113438883B (en) | Preparation method and application of binary heterostructure wave-absorbing material molybdenum oxide-molybdenum phosphide | |
| Hang et al. | High-performance composite elastomers with abundant heterostructures for enhanced electromagnetic wave absorption with ultrabroad bandwidth | |
| Lv et al. | MXene/bimetallic CoNi-MOF derived magnetic-dielectric balanced composites with multiple heterogeneous interfaces for excellent microwave absorption | |
| CN111393845B (en) | Chiral polypyrrole/Fe 3 O 4 Preparation method and application of graphene composite material | |
| CN108538621B (en) | A kind of Cu/CuO@Ni (OH) of core-shell structure2Electrode material and preparation method thereof | |
| He et al. | A control strategy for microwave absorption performance on a two-dimensional scale | |
| CN111009422B (en) | Nickel-based NiCo with core-shell structure2O4Preparation method of polyaniline nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |