CN115028847A - CoNi alloy MOF porous material and preparation and application thereof - Google Patents
CoNi alloy MOF porous material and preparation and application thereof Download PDFInfo
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- 229910002441 CoNi Inorganic materials 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 51
- 239000011148 porous material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims abstract description 12
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract description 12
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- QURGMSIQFRADOZ-UHFFFAOYSA-N 5-(3,5-dicarboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 QURGMSIQFRADOZ-UHFFFAOYSA-N 0.000 claims description 2
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a CoNi alloy MOF porous material and preparation and application thereof, wherein the porous material is prepared by the following processes: (1) adding cobalt acetate tetrahydrate, nickel acetate tetrahydrate and an organic linking agent into absolute ethyl alcohol, and stirring for dissolving to obtain a transparent mixed solution; (2) transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction, washing and drying the obtained reaction product to obtain precursor powder; (3) and (3) placing the precursor powder in an inert atmosphere for high-temperature reduction, and then cooling to room temperature to obtain the target product. The invention can obtain product particles with better dispersity and uniform appearance and particle size, can keep the original appearance more completely after being reduced at high temperature in nitrogen atmosphere, and has no obvious agglomeration phenomenon. Meanwhile, the CoNi alloy MOF porous material shows excellent performance in the fields of microwave absorption, catalysis, sensors and the like.
Description
Technical Field
The invention belongs to the technical field of functional materials, and relates to a CoNi alloy MOF porous material, and preparation and application thereof.
Background
A Metal-organic Framework (MOF) material is formed by self-assembling Metal ions and organic ligands through coordination bonds, and is an exciting crystalline porous material in a novel material. The MOF material has a highly regular topological structure and periodic network channels, and is widely applied to the fields of gas storage, catalysis, electronic conduction materials, sensors, electromagnetic interference resistance and the like. However, the pure MOF has low conductive and dielectric properties and cannot meet the requirement of electromagnetic impedance matching; and the MOF material is easy to agglomerate, and the reactive sites of the MOF material cannot be fully exposed, so that the application of the MOF material is limited to a certain extent. In order to improve the conductivity of MOFs and solve the agglomeration phenomenon, thermal annealing of MOF precursors is one of the strategies to obtain porous metal carbon-based nanostructured materials, and by selecting different metal sources and organic linkers, the final components of MOF derivatives can be effectively regulated, and due to the diversified components and good chemical homogeneity of MOFs, many efforts have been made to prove that MOFs are ideal templates for manufacturing multifunctional inorganic functional materials.
The CoNi alloy has been widely studied due to its special physical and chemical properties, and is suitable for various fields such as microwave absorption, catalysis, hydrogen storage, biomedical micro devices, magnetic resonance imaging agents and the like. The application of the CoNi alloy is influenced by two factors of composition and morphology, because the difference of the composition and the morphology leads to the change of the inherent magnetic moment, the magnetic permeability and the magnetism of the alloy material. The CoNi alloy with single component has the phenomena of high density, easy oxidation, easy agglomeration and the like. Therefore, when the microwave absorbing material interacts with electromagnetic waves, the microwave absorbing material has the defect of single electromagnetic loss mechanism, and is difficult to simultaneously meet the problems of attenuation and impedance matching, so that the microwave absorbing performance is not ideal. When the catalyst is used, the agglomeration of the CoNi alloy causes a great reduction of the active sites of the catalyst, thereby reducing the catalytic activity of the catalyst. Therefore, if the shape or character of the alloy material can be modified by using the material with special performance, the specific surface area, the chemical stability, the electron conduction rate and the like of the alloy material can be improved, and the application performance of the alloy material can be further effectively enhanced.
Disclosure of Invention
The invention aims to provide a CoNi alloy MOF porous material, and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a CoNi alloy MOF porous material, which comprises the following steps:
(1) adding cobalt acetate tetrahydrate, nickel acetate tetrahydrate and an organic linking agent into absolute ethyl alcohol, and stirring for dissolving to obtain a transparent mixed solution;
(2) transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction, washing and drying the obtained reaction product to obtain precursor powder;
(3) and (3) placing the precursor powder in an inert atmosphere for high-temperature reduction, and then cooling to room temperature to obtain the target product.
Further, in the step (1), the organic linking agent is any one of polyvinylpyrrolidone (PVP-K30), 2-methylimidazole, terephthalic acid, and 3,3 ', 5, 5' -biphenyltetracarboxylic acid.
Further, in the step (1), the mass ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and organic connecting agent is (1-6): (1-3): (3-23).
Further, in the step (1), the addition amount of the absolute ethyl alcohol satisfies the following condition: ni in mixed solution 2+ The concentration is 1-4 g/L.
Further, in the step (2), the temperature of the hydrothermal reaction is 60-130 ℃, and the time is 5-12 hours.
Further, in the step (2), the washing process is as follows: and adopting deionized water and ethanol to centrifugally wash for several times at the rotating speed of 8000-10000 rpm.
Further, in the step (2), the drying process specifically comprises: and (3) drying in vacuum at the temperature of 60-80 ℃.
Further, in the step (3), the temperature of high-temperature reduction is 400-600 ℃, and the time is 1-3 h.
Further, the inert atmosphere is a nitrogen atmosphere.
The second technical scheme of the invention provides a CoNi alloy MOF porous material which is prepared by the preparation method and is characterized in that the CoNi alloy MOF porous material is in a cubic fluffy shape, the size is 0.4-0.6 mu m, and a regular ordered pore structure is distributed on the surface.
The third technical scheme of the invention provides application of a CoNi alloy MOF porous material, and the CoNi alloy MOF porous material is used in the fields of microwave absorption, catalysis or sensors.
The invention adopts an efficient and simple solvothermal reaction method to synthesize the CoNi-MOF precursor, can obtain product particles with better dispersity and uniform appearance and particle size by simply adjusting the type of the organic connecting agent, can still keep the original appearance more completely after being reduced at high temperature in a nitrogen atmosphere, and has no obvious agglomeration phenomenon. Meanwhile, the CoNi alloy MOF porous material shows excellent performance in the fields of microwave absorption, catalysis, sensors and the like.
Compared with the prior art, the preparation method of the CoNi alloy MOF porous material is simple and convenient, is easy to operate, and has relatively mild and easily controlled preparation conditions. The obtained CoNi alloy MOF is in a cubic shape and is distributed with regular pore channels, so that the CoNi alloy MOF has a large specific surface area and high porosity, and has attractive application prospects in the aspects of gas adsorption, biosensing, catalysis, electromagnetic interference and the like. In addition, the method can effectively solve the surface agglomeration phenomenon by adjusting the organic connecting agent for forming the MOF, thereby fully exposing the reactive sites and enhancing the application capability of the reactive sites.
Drawings
FIG. 1 is a scanning electron micrograph and a transmission electron micrograph of example 1: (a1) example 1-scanning electron micrograph of a precursor of a CoNi alloy MOF; (a2) example 1-high power scanning electron micrograph and outline schematic of a precursor of a CoNi alloy MOF; (b1) example 1-scanning electron micrograph of CoNi alloy MOF porous material; (b2) example 1-high power scanning electron micrograph of a CoNi alloy MOF porous material; (c1) example 1-transmission electron micrograph of a CoNi alloy MOF porous material; (c2) example 1-high power transmission electron micrograph of CoNi alloy MOF porous material.
FIG. 2 is a transmission electron micrograph of examples 2 to 4: (a) example 2-transmission electron micrograph of a precursor of a CoNi alloy MOF; (b) example 3-Transmission Electron microscopy of CoNi alloy MOF precursors; (c) example 4-Transmission Electron microscopy of CoNi alloy MOF precursors.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Raw materials for sale or conventional processing techniques.
Example 1:
preparation of a CoNi alloy MOF porous material:
first, 0.84g of cobalt acetate tetrahydrate, 0.42g of nickel acetate tetrahydrate and 3g of PVP-K30 were weighed and added to 160mL of anhydrous ethanol, and sufficiently stirred and dissolved to obtain a transparent mixed solution.
The clear solution was then transferred to a teflon lined stainless steel hydrothermal reaction kettle and heated at 90 ℃ for 6 h. And cooling to room temperature, centrifugally washing with deionized water for several times, vacuum drying at 70 ℃, and collecting to obtain CoNi alloy MOF precursor powder.
Finally, the precursor powder is placed in a porcelain boat and placed in a tube furnace under the protection of inert gas nitrogen at the speed of 2 ℃/min -1 The temperature rise rate is increased to 500 ℃, the reduction is carried out for 2h at high temperature, and after the temperature is naturally reduced to room temperature, the obtained CoNi alloy MOF porous material is in a cubic fluffy shape, the size is 0.4-0.6 mu m, and a regular ordered pore structure is distributed on the surface.
Example 2:
compared to example 1, most of them are the same except that in this example: the organic linking agent used was terephthalic acid.
Example 3:
compared to example 1, most of them are the same except that in this example: the organic linking agent is 2-methylimidazole.
Example 4:
compared to example 1, most of them are the same except that in this example: the organic linking agent is 3,3,5, 5' -biphenyltetracarboxylic acid.
The microstructure of the CoNi alloy MOF porous material with controllable morphology in the above example was characterized by scanning electron microscopy (SEM, Hitachi FE-SEM S-4800), and the powder sample was coated on the surface of the conductive adhesive for testing. The microstructure information of a series of alloy materials is characterized by a transmission electron microscope (TEM, JEOL JEM-2100F), and a powder sample is ultrasonically dispersed in ethanol and then dropped on a carbon-supported copper net for drying to test.
FIG. 1 is a scanning electron micrograph and a transmission electron micrograph of the CoNi alloy MOF precursor synthesized in example 1, wherein the precursor is a cube with pyramid-shaped ends, the length is about 1.5-3 μm, the side length is 0.4-0.6 μm, and the surface is smooth. The sample has uniform particle size distribution and good dispersibility. The CoNi alloy MOF subjected to high-temperature reduction has no great change in appearance and size, but has a rough surface, a large number of ordered pore paths are distributed in the surface, and the particle size of the whole sample is uniformly distributed and has good dispersibility. The microwave absorbing material is used as a microwave absorbing agent, the effective wave absorbing frequency range is 10-14GHz, and when the thickness is 2.6mm, the reflection loss reaches the minimum of-53 dB.
Compared with example 1, the morphology of the precursor of the CoNi alloy MOF is greatly changed due to the change of the kind of the organic linking agent. As shown in fig. 2, when the organic linking agent is terephthalic acid, the precursor of the CoNi alloy MOF is in a cube shape, the side length is about 0.5 μm, the surface is smooth, the particle size of the sample is uniform, but the agglomeration is serious. When the organic connecting agent is 2-methylimidazole, the precursor of the CoNi alloy MOF is spherical, the grain diameter is about 0.2-0.3 mu m, the uniformity and the dispersity of the grain diameter of a sample are good, and the agglomeration is still generated. When the organic connecting agent is 3,3,5, 5' -biphenyltetracarboxylic acid, the precursor of the CoNi alloy MOF is in a square shape, the particle size distribution and the dispersity of a sample are poor, and the agglomeration phenomenon is serious. Therefore, the selection of the type of organic linking agent has a significant influence on the morphology, particle size and dispersibility of the sample.
Example 5:
compared to example 1, most of them are the same except that in this example: the mass ratio of the addition amounts of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and PVP-K30 is 1.26 g: 0.42 g: 4.2g, Ni 2+ The concentration was 1.0 g/L.
Example 6:
compared to example 1, most of them are the same except that in this example: the mass ratio of the addition amounts of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and PVP-K30 is 2.1 g: 0.84 g: 6.3g, Ni 2+ The concentration was 2.6 g/L.
Example 7:
with fruitExample 1 compared, most of the same, except in this example: the mass ratio of the addition amounts of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and PVP-K30 is 2.52 g: 1.26 g: 7.56g, Ni 2+ The concentration was 3.0 g/L.
Example 8:
compared to example 1, most of them are the same except that in this example: the mass ratio of the addition amounts of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and PVP-K30 is 1.68 g: 1.26 g: 9.66g, Ni 2+ The concentration was 4.0 g/L.
Example 9:
most of the results were the same as those in example 1, except that the hydrothermal reaction temperature was adjusted to 60 ℃ and the reaction time was 12 hours.
Example 10:
most of the results were the same as those in example 1, except that the hydrothermal reaction temperature was adjusted to 80 ℃ and the reaction time was adjusted to 9 hours.
Example 11:
compared to example 1, most of them are the same except that in this example: the temperature of the hydrothermal reaction is adjusted to 100 ℃ and the reaction time is 6 h.
Example 12:
compared to example 1, most of them are the same except that in this example: the temperature of the hydrothermal reaction is adjusted to 130 ℃ and the reaction time is 5 h.
Example 13:
most of them were the same as in example 1, except that in this example, the temperature of the high-temperature reduction was adjusted to calcination at 400 ℃ for 3 hours.
Example 14:
most of them were the same as in example 1, except that in this example, the temperature of the high-temperature reduction was adjusted to calcination at 600 ℃ for 1 hour.
Example 15:
compared to example 1, most of them are the same except that in this example: adjusting the mass of cobalt acetate tetrahydrate and organic connecting agent to ensure that the mass ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and organic connecting agent is 1: 1: 3.
example 16:
compared to example 1, most of them are the same except that in this example: adjusting the mass of the cobalt acetate tetrahydrate and the organic connecting agent so that the mass ratio of the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate and the organic connecting agent is 6: 3: 23.
the embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a CoNi alloy MOF porous material is characterized by comprising the following steps:
(1) adding cobalt acetate tetrahydrate, nickel acetate tetrahydrate and an organic linking agent into absolute ethyl alcohol, and stirring for dissolving to obtain a transparent mixed solution;
(2) transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction, washing and drying the obtained reaction product to obtain precursor powder;
(3) and (3) placing the precursor powder in an inert atmosphere for high-temperature reduction, and then cooling to room temperature to obtain the target product.
2. The method for preparing the CoNi alloy MOF porous material according to claim 1, wherein in the step (1), the organic linking agent is any one of polyvinylpyrrolidone, 2-methylimidazole, terephthalic acid and 3,3 ', 5, 5' -biphenyltetracarboxylic acid.
3. The preparation method of the CoNi alloy MOF porous material according to claim 1, wherein in the step (1), the mass ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and organic connecting agent is (1-6): (1-3): (3-23).
4. The method for preparing the CoNi alloy MOF porous material according to claim 1, wherein in the step (1), the addition amount of the absolute ethyl alcohol is as follows: ni in mixed solution 2+ The concentration is 1-4 g/L.
5. The preparation method of the CoNi alloy MOF porous material according to claim 1, wherein in the step (2), the temperature of the hydrothermal reaction is 60-130 ℃ and the time is 5-12 h.
6. The method for preparing the CoNi alloy MOF porous material according to the claim 1, wherein in the step (2), the washing process is as follows: and adopting deionized water and ethanol to centrifugally wash for several times at the rotating speed of 8000-10000 rpm.
7. The method for preparing the CoNi alloy MOF porous material according to claim 1, wherein in the step (2), the drying process is specifically as follows: and (3) drying in vacuum at the temperature of 60-80 ℃.
8. The preparation method of the CoNi alloy MOF porous material according to claim 1, wherein in the step (3), the temperature of high-temperature reduction is 400-600 ℃ and the time is 1-3 h.
9. The CoNi alloy MOF porous material is prepared by the preparation method according to any one of claims 1 to 8, and is characterized in that the CoNi alloy MOF porous material is in a cubic fluffy shape, the size of the CoNi alloy MOF porous material is 0.4-0.6 μm, and a regular ordered pore structure is distributed on the surface of the CoNi alloy MOF porous material.
10. The use of a CoNi alloy MOF porous material of claim 9 in the fields of microwave absorption, catalysis or sensors.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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