CN114727576A - Metal organic framework/conductive polymer derived nano material with electromagnetic wave absorption performance and preparation method and application thereof - Google Patents
Metal organic framework/conductive polymer derived nano material with electromagnetic wave absorption performance and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electromagnetic wave absorption materials, in particular to a metal organic framework/conductive polymer derived nano material with electromagnetic wave absorption performance and a preparation method and application thereof. The metal organic framework/conductive polymer derived nano material comprises a first carbon structure, a second carbon structure and a metal simple substance; the first carbon structure has a network structure and is formed by pyrolysis of conductive polyaniline; the second carbon structure and the metal simple substance are formed by pyrolyzing a metal organic framework, the metal simple substance is dispersed in the second carbon structure, and an integral structure formed by the second carbon structure and the metal simple substance is loaded on the first carbon structure. The invention forms a net structure by pyrolyzing conductive polyaniline, and loads carbon and metal simple substance derived from the metal organic framework, wherein the conductive polyaniline has wider response frequency band compared with other conductive polymers, and the effective absorption frequency band of the metal organic framework/conductive polymer derived nano material to electromagnetic waves is widened.
Description
Technical Field
The invention relates to the technical field of electromagnetic wave absorption materials, in particular to a metal organic framework/conductive polymer derived nano material with electromagnetic wave absorption performance and a preparation method and application thereof.
Background
In recent years, with the development of science and technology, products such as household appliances, mobile terminals, urban rails, high-speed rails, high-voltage power grids and the like have deepened into daily life of people, convenience is brought to people, certain electromagnetic radiation is accompanied, and meanwhile electromagnetic wave transmitting equipment with high power, such as signal towers for broadcasting and televisions and the like, are arranged in areas with high population density, so that increasingly serious electromagnetic wave pollution is gradually paid more attention to the people. The effects of these electromagnetic wave emitting devices mainly include two aspects: firstly, the generated electromagnetic waves can interfere with other electronic equipment and instruments; secondly, certain high-power electromagnetic waves can damage the safety and health of human bodies. Compared with solid waste pollution, air pollution, water pollution, noise pollution and other types of pollution, electromagnetic wave pollution is more common and more difficult to treat, so that the research on the prevention and treatment of the electromagnetic wave pollution is particularly important. With the rapid development of detection technologies such as radar, researchers are dedicated to the research of radar stealth technology, the reflection of radar waves is reduced, and the development of wave-absorbing materials provides possibility for the target.
Metal Organic Framework (MOF) type materials are a porous material emerging in recent 20 years. MOFs are often formed by strong coordination of immobilized metal atoms or metal atom clusters with nitrogen-containing organic ligands (amines, phenols, sulfonic acids, phosphoric acids, carboxylic acids, nitriles), with a porous topology in the form of an ordered network of spatially infinite extent.
Although the traditional microwave absorption nano materials make great progress in magnetic loss or dielectric loss, the defects of high density, single mechanism and the like exist, and the development and large-scale use of the materials are seriously hindered. The porous carbon structure derived from the MOF is beneficial to reducing the density of the wave-absorbing material, and the light porous carbon material with a special microstructure can be prepared by calcining the porous carbon structure at high temperature, wherein metal and/or metal oxide nano particles generated by calcining are also contained. The calcined product of the MOF material has excellent wave-absorbing performance and effective bandwidth due to rich electromagnetic loss mechanisms, so that the MOF material is widely concerned by researchers.
The MOF derived material refers to a material obtained by taking MOF as a precursor or template through a series of post-treatment processes (high-temperature heat treatment, surface modification, chemical modification and the like). The synthesis of MOF derived materials involves two steps: designing and synthesizing suitable MOF precursors; the target material with a specific composition, morphology, structure is obtained by a specific post-treatment process, such as pyrolysis. On one hand, graphite carbon can be obtained by means of the catalytic action of metal in the pyrolysis process, so that the obtained material has stronger dielectric loss. On the other hand, magnetic metals can impart additional magnetic losses to the material. The MOF-based core-shell structure wave-absorbing material can realize the attenuation of electromagnetic waves through the synergistic effect among different components, enhanced dielectric loss, additional magnetic loss, improved impedance matching and increased interface polarization loss.
However, the effective absorption band (effective absorption frequency range) of the existing MOF-derived materials is generally narrow, and cannot effectively absorb different electromagnetic waves.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a metal organic framework/conductive polymer derived nano material which has the advantages of low structural density, uniform pores, abundant electromagnetic loss mechanisms, wide effective absorption frequency band and strong reflection loss characteristic, and can well absorb electromagnetic waves.
The invention also provides a preparation method and application of the metal organic framework/conducting polymer derived nano material.
Specifically, the invention adopts the following technical scheme:
the first aspect of the invention provides a metal organic framework/conductive polymer derived nanomaterial, which comprises a first carbon structure, a second carbon structure and a metal simple substance;
the first carbon structure has a network structure and is formed by pyrolysis of conductive polyaniline;
the second carbon structure and the metal simple substance are formed by pyrolyzing a metal organic framework, the metal simple substance is dispersed in the second carbon structure, and an integral structure formed by the second carbon structure and the metal simple substance is loaded on the first carbon structure.
According to the invention, a mesh structure is formed by pyrolysis of conductive polyaniline, and carbon and a metal simple substance derived from the metal organic framework are loaded, wherein the conductive polyaniline has a wider response frequency band compared with other conductive polymers, so that the effective absorption frequency band of the metal organic framework/conductive polymer derived nano material on electromagnetic waves is widened, the metal organic framework/conductive polymer derived nano material can have strong reflection loss characteristics on electromagnetic waves with different frequencies, and the electromagnetic waves can be well absorbed.
In some examples of the present invention, the elemental metal comprises at least one of Fe, Co, Cu, Zn, and Ni.
In some examples of the present invention, the second carbon structure has at least one of a rhombohedral structure and a cubic structure. The second carbon structure is determined by the structure of the metal organic framework, and different second carbon structures can be obtained by adopting different metal organic frameworks.
In some examples of the invention, the metal organic framework comprises at least one of ZIF-67, ZIF-8.
The second aspect of the present invention provides a method for preparing the metal organic framework/conductive polymer derived nanomaterial, comprising the following steps:
growing a metal organic framework on the conductive polyaniline in situ to obtain a polyaniline/metal organic framework composite material;
and pyrolyzing the polyaniline/metal organic framework composite material to obtain the metal organic framework/conductive polymer derived nano material.
In some examples of the present invention, the conductive polyaniline is prepared by: and in the presence of protonic acid, aniline is subjected to polymerization reaction to obtain the conductive polyaniline. Polyaniline obtained by polymerizing aniline alone is non-conductive, and the electric conductivity of polyaniline material can be rapidly improved by adding protonic acid in the polymerization process of aniline monomer, generally by several orders of magnitude or even more than 10 orders of magnitude, to obtain conductive polyaniline. The conductive polyaniline obtained by polymerization can be directly used for in-situ growth of a metal organic framework after being dried, and does not need to use alkaline solution or other reagents for surface treatment.
In some examples of the invention, the protic acid comprises at least one of hydrochloric acid, sulfuric acid, acetic acid, sulfonic acid.
In some embodiments of the present invention, the concentration of the protonic acid in the polymerization reaction system of aniline is 0.5 to 3mol/L, preferably 1 to 2 mol/L.
In some embodiments of the invention, the aniline is polymerized in the presence of an initiator comprising at least one of ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile, preferably ammonium persulfate, potassium persulfate.
In some embodiments of the invention, the aniline to initiator ratio is 1 mL: 0.5-5 g, preferably 1 mL: 1-4 g, more preferably 1 mL: 2-3 g.
In some embodiments of the invention, the polymerization temperature is from-10 to 10 deg.C, preferably from-5 to 5 deg.C, and more preferably 0 deg.C.
In some embodiments of the invention, the polymerization time is 0.5 to 5 hours, preferably 1 to 2 hours.
In some embodiments of the present invention, the step of growing the metal-organic framework in situ on the conductive polyaniline comprises: in an organic solvent, mixing conductive polyaniline with a precursor of a metal organic framework, wherein the precursor of the metal organic framework forms the metal organic framework in situ on the conductive polyaniline. Experiments show that the precursor can form a metal organic framework on the conductive polyaniline in situ only in an organic solvent.
In some examples of the invention, the precursor of the metal-organic framework comprises a metal salt, a surfactant and an organic ligand.
In some embodiments of the present invention, the step of growing the metal-organic framework in situ on the conductive polyaniline comprises: impregnating conductive polyaniline by using organic solution of metal salt and surfactant to obtain pre-impregnated solution; and mixing the organic ligand solution with the preimpregnation solution, and reacting under stirring to obtain the polyaniline/metal organic framework composite material.
In some examples of the invention, the metal organic framework comprises at least one of ZIF-67, ZIF-8.
In some embodiments of the invention, the metal salt comprises a salt of at least one metal selected from Fe, Co, Cu, Zn, Ni. The salt comprises at least one of nitrate, nitrite, sulfate and chloride; the surfactant comprises at least one of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate; the organic ligand comprises at least one of 2-methylimidazole and formic acid. Different precursors can be selected adaptively according to different kinds of metal organic frameworks. For example, when the metal organic framework is ZIF-67, the corresponding metal salt is a nitrate, nitrite, sulfate or chloride salt of Co, the surfactant is polyvinylpyrrolidone, and the organic ligand is 2-methylimidazole.
Meanwhile, the amount of each precursor can also be determined according to the general technique. As an example, when the metal organic framework is ZIF-67, the molar ratio of the metal element to the organic ligand in the metal salt is 1: 5-10, preferably 1: 6-9, more preferably 1: 7 to 8. The ratio of the metal element in the metal salt to the surfactant is 1 mol: 1-10 g, preferably 1 mol: 2-5 g, for example 1 mol: 4g of the total weight. The invention can generate the metal organic framework on the conductive polyaniline under the condition of low dosage of the surfactant, and compared with the prior art, the invention obviously reduces the use of the surfactant.
In some embodiments of the invention, the temperature of the in-situ grown metal organic framework is 0 to 50 ℃, preferably 10 to 30 ℃; the time is 5-20 h, preferably 10-15 h.
In some embodiments of the invention, the organic solvent comprises at least one of methanol, ethanol, N-Dimethylformamide (DMF), acetone, preferably methanol.
In some examples of the present invention, the ratio of the metal element in the metal salt to the polyaniline is 1 mol: 10-120 g, preferably 1 mol: 10 to 100g, more preferably 1 mol: 10 to 80g, more preferably 1 mol: 20 to 50g, more preferably 1 mol: 23-46 g.
In some examples of the invention, the temperature for pyrolyzing the polyaniline/metal organic framework composite material is 600-1000 ℃, preferably 600-900 ℃, such as 600 ℃, 700 ℃, 800 ℃, 900 ℃; the time is 2-10 h, preferably 5-8 h.
In some examples of the invention, the temperature rise rate of the pyrolysis process is 0.5-3 ℃/min. Preferably, the temperature rise rate is: 2-2.5 ℃/min below 460 ℃, and 0.5-1.5 ℃/min above 460 ℃.
In some examples of the invention, the pyrolysis is carried out in a protective atmosphere, such as a nitrogen, argon atmosphere.
The third aspect of the present invention provides the application of the metal organic framework/conducting polymer derived nano material in electromagnetic wave absorption.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, polyaniline is selected to load the metal organic framework, a reticular carbon structure is formed after pyrolysis, and the conductive polyaniline has a wider response frequency band compared with other conductive polymers, so that the metal organic framework/conductive polymer derivative nano material has a wider effective absorption frequency band compared with the existing material. In addition, the relaxation phenomenon of polyaniline has a positive effect on improving the wave absorbing performance, and the polyaniline has the advantages of low density, easy preparation, excellent environmental stability and the like, and is beneficial to preparing materials with low structural density.
Meanwhile, the preparation method is simple and strong in adjustability, the content of magnetic metal in the derived cobalt-based wave-absorbing material and the morphology of the carbon skeleton can be effectively adjusted and controlled by changing the pyrolysis conditions, the optimization of complex permeability and complex dielectric constant is promoted, the impedance matching degree is improved, and the reduction of reflection loss under low thickness and the broadening of an effective absorption band are further realized.
Drawings
FIG. 1 is an SEM image of Z/P-801 of example 1;
FIG. 2 shows the results of the EDS Probe test for Z/P-801 of example 1
FIG. 3 is an XRD pattern of Z/P-801 of example 1;
FIG. 4 is a Raman spectrum image of Z/P-801 of example 1;
FIG. 5 is a reflection loss curve of Z/P-801 of example 1;
FIG. 6 is an SEM image of Z/P-802 of example 2;
FIG. 7 is an SEM image of Z/P-803 of example 3;
FIG. 8 is an SEM image of Z/P-701 of example 4;
FIG. 9 is an SEM image of Z/P-809 for comparative example 1;
FIG. 10 is a reflection loss curve of Z/P-809 for comparative example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.
Example 1
A metal organic framework/conductive polymer derived nano material is prepared by the following steps:
(1) 4.7mL of aniline and 50mL of 2mol/L hydrochloric acid were added to a three-necked flask, and stirred in an ice-water bath for 1 hour. 11.4g of ammonium persulfate was dissolved in 25mL of deionized water and added to the three-necked flask using a dropping funnel over a period of about 30 min. The reaction was followed for 1h, taking care to maintain the temperature. And then washing and drying to obtain the conductive polyaniline.
(2) 1.1640g of cobalt nitrate hexahydrate is dissolved in 60mL of methanol, and ultrasonic dispersion is carried out for 10 minutes; dissolving 0.0400g of polyvinylpyrrolidone in 10mL of methanol, and ultrasonically dispersing for 10 minutes; the two solutions were sequentially dropped into 0.0920g of dried polyaniline, and reacted for 6 hours under magnetic stirring at room temperature to obtain a prepreg solution.
(3) 2.6272g of 2-methylimidazole was dissolved in 60mL of methanol, and the solution was dispersed with ultrasound for 10 minutes, dropped into the prepreg solution, and reacted for 12 hours with magnetic stirring at room temperature. Centrifuging and washing for 3 times by using methanol, collecting a centrifugal product, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain the conductive polyaniline powder with the ZIF-67 particles growing on the surface.
(4) Grinding conductive polyaniline powder with ZIF-67 particles growing on the surface, putting the ground conductive polyaniline powder into a nitrogen-filled tube furnace for pyrolysis at 800 ℃, wherein the heating rate is 2 ℃/min below 460 ℃ and 1 ℃/min above 460 ℃, the heat preservation time is 6 hours, cooling along with the furnace, and grinding to obtain the metal organic framework/conductive polymer derived nanomaterial, which is in a black powder shape and is marked as Z/P-801.
The SEM image of Z/P-801 is shown in FIG. 1, and it can be seen that ZIF-67 particles grow in situ on the surface of polyaniline and are firmly attached, the Co/C composite material formed by sintering ZIF-67 still completely maintains the rhombic dodecahedron structure of the precursor, and small particles are uniformly dispersed on the surface; the sintered product of polyaniline is a net structure with uniform pores. FIG. 2 is the EDS probe test result accompanying SEM, and it can be seen that surface cobalt element is substantially present only on the rhombic dodecahedron particles formed after ZIF-67 sintering, as expected.
The XRD pattern of Z/P-801 is shown in fig. 3, and the pattern has three distinct diffraction peaks (2 θ ═ 44.2 °, 51.6 ° and 76.0 °), corresponding to the (111), (200) and (220) crystal planes of face-centered cubic (fcc) cobalt, respectively, thereby demonstrating the formation of elemental cobalt.
Raman spectrum image of Z/P-801 is shown in FIG. 4, and the image has two distinct peaks, respectively located at 1350cm centers-1And 1590cm-1Sequentially corresponding to a D peak and a G peak, wherein the D peak corresponds to defects and disorder induction in the carbon material, and the G peak corresponds to all sp in carbon ring and long chain of the carbon component2Induction of key vibration, ID/IG0.929, indicating that the sample has a high degree of graphitization, which is conducive to the formation of a good conductive network.
And (3) testing the reflection loss of the Z/P-801 by using a vector network analyzer and adopting a coaxial transmission line method. Before testing, paraffin and a Z/P-801 powder sample are uniformly mixed at 70 ℃ according to a selected mass ratio (the mass fraction of the powder is 40 percent, namely the filling degree), the mixture is added into a prefabricated mold, the mixture is pressed into test rings (the inner diameter is 3mm, the outer diameter is 7mm) with different thicknesses, the thickness d of the test rings is measured by a vernier caliper, the electromagnetic parameters of the test rings are measured, and the Reflection Loss (RL) curve of the Z/P-801 is obtained by calculation and is shown in figure 5, the effective absorption frequency range (the frequency band with the reflection loss reaching-10 dB) under the conditions that the filling degree is 40 wt% and the thickness is 7.0mm is 15.76-17.76 GHz, wherein the reflection loss peak value at the frequency of 16.72GHz can reach-39.45 dB.
Example 2
The preparation method of the metal organic framework/conductive polymer derived nanomaterial is different from that of the nanomaterial in the embodiment 1 in that the dosage of polyaniline in the step (2) is increased, and the specific steps are as follows:
(1) 4.7mL of aniline and 50mL of 2mol/L hydrochloric acid were added to a three-necked flask, and stirred in an ice-water bath for 1 hour. 11.4g of ammonium persulfate was dissolved in 25mL of deionized water and added to the three-necked flask using a dropping funnel over a period of about 30 min. The reaction was followed for 1h, taking care to maintain the temperature. And then washing and drying to obtain the conductive polyaniline.
(2) 1.1640g of cobalt nitrate hexahydrate is dissolved in 60mL of methanol, and ultrasonic dispersion is carried out for 10 minutes; dissolving 0.0400g of polyvinylpyrrolidone in 10mL of methanol, and ultrasonically dispersing for 10 minutes; the two solutions were sequentially dropped into 0.1380g of dried polyaniline, and reacted for 6 hours under magnetic stirring at room temperature to obtain a prepreg solution.
(3) 2.6272g of 2-methylimidazole was dissolved in 60mL of methanol, and the solution was dispersed with ultrasound for 10 minutes, dropped into the prepreg solution, and reacted for 12 hours with magnetic stirring at room temperature. Centrifuging and washing for 3 times by using methanol, collecting a centrifugal product, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain the conductive polyaniline powder with the ZIF-67 particles growing on the surface.
(4) Grinding conductive polyaniline powder with ZIF-67 particles growing on the surface, putting the ground conductive polyaniline powder into a nitrogen-filled tube furnace for pyrolysis at 800 ℃, wherein the heating rate is 2 ℃/min below 460 ℃ and 1 ℃/min above 460 ℃, the heat preservation time is 6 hours, cooling along with the furnace, and grinding to obtain the metal organic frame/conductive polymer derived composite nano wave-absorbing material which is in a black powder shape and is marked as Z/P-802.
As shown in FIG. 6, the SEM image of Z/P-802 shows that distinct rhombic dodecahedral particles with small nanoscale particles attached thereto were observed, and the structural morphology was similar to that of Z/P-801 of example 1. The Z/P-802 reflection loss curve was tested to be similar to that of example 1.
Example 3
The preparation method of the metal organic framework/conductive polymer derived nanomaterial is different from that of the nanomaterial in the embodiment 1 in that the dosage of polyaniline in the step (2) is increased, and the specific steps are as follows:
(1) 4.7mL of aniline and 50mL of 2mol/L hydrochloric acid were added to a three-necked flask, and stirred in an ice-water bath for 1 hour. 11.4g of ammonium persulfate was dissolved in 25mL of deionized water and added to the three-necked flask using a dropping funnel over a period of about 30 min. The reaction was followed for 1h, taking care to maintain the temperature. And then washing and drying to obtain the conductive polyaniline.
(2) 1.1640g of cobalt nitrate hexahydrate is dissolved in 60mL of methanol, and ultrasonic dispersion is carried out for 10 minutes; dissolving 0.0400g of polyvinylpyrrolidone in 10mL of methanol, and performing ultrasonic dispersion for 10 minutes; the two solutions were sequentially dropped into 0.1840g of dried polyaniline, and reacted for 6 hours under magnetic stirring at room temperature to obtain a prepreg solution.
(3) 2.6272g of 2-methylimidazole was dissolved in 60mL of methanol, and the solution was ultrasonically dispersed for 10 minutes, and the solution was dropped into the prepreg solution, and the reaction was continued for 12 hours under magnetic stirring at room temperature. Centrifuging and washing for 3 times by using methanol, collecting a centrifugal product, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain the conductive polyaniline powder with the ZIF-67 particles growing on the surface.
(4) Grinding conductive polyaniline powder with ZIF-67 particles growing on the surface, putting the ground conductive polyaniline powder into a nitrogen-filled tubular furnace for pyrolysis at 800 ℃, wherein the heating rate is 2 ℃/min below 460 ℃ and 1 ℃/min above 460 ℃, the heat preservation time is 6 hours, cooling along with the furnace, and grinding to obtain the metal organic frame/conductive polymer derived composite nano wave-absorbing material, which is in a black powder shape and is marked as Z/P-803.
As shown in FIG. 7, the SEM image of Z/P-803 shows that distinct rhombic dodecahedral particles are observed, and nanoscale small particles are attached to the particles, and the structural morphology of the particles is similar to that of Z/P-801 in example 1. The Z/P-803 reflection loss curve was tested to be similar to that of example 1.
Example 4
A metal organic framework/conducting polymer derived nanomaterial, which is prepared by a method different from that of example 1 in that the amount of polyaniline used in step (2) is increased and the pyrolysis temperature in step (4) is lowered. The method comprises the following specific steps:
(1) 4.7mL of aniline and 50mL of 2mol/L hydrochloric acid were added to a three-necked flask, and stirred in an ice-water bath for 1 hour. 11.4g of ammonium persulfate was dissolved in 25mL of deionized water and added to the three-necked flask using a dropping funnel over a period of about 30 min. The reaction was followed for 1h, taking care to maintain the temperature. And then washing and drying to obtain the conductive polyaniline.
(2) 1.1640g of cobalt nitrate hexahydrate is dissolved in 60mL of methanol, and ultrasonic dispersion is carried out for 10 minutes; dissolving 0.0400g of polyvinylpyrrolidone in 10mL of methanol, and ultrasonically dispersing for 10 minutes; the two solutions were sequentially dropped into 0.1150g of dried polyaniline, and reacted for 6 hours under magnetic stirring at room temperature to obtain a prepreg solution.
(3) 2.6272g of 2-methylimidazole was dissolved in 60mL of methanol, and the solution was ultrasonically dispersed for 10 minutes, and the solution was dropped into the prepreg solution, and the reaction was continued for 12 hours under magnetic stirring at room temperature. Centrifuging and washing for 3 times by using methanol, collecting a centrifugal product, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain the conductive polyaniline powder with the ZIF-67 particles growing on the surface.
(4) Grinding conductive polyaniline powder with ZIF-67 particles growing on the surface, putting the ground conductive polyaniline powder into a nitrogen-filled tube furnace for pyrolysis at 700 ℃, wherein the heating rate is 2 ℃/min below 460 ℃ and 1 ℃/min above 460 ℃, the heat preservation time is 6 hours, cooling along with the furnace, and grinding to obtain the metal organic frame/conductive polymer derived composite nano wave-absorbing material, which is in a black powder shape and is marked as Z/P-701.
As shown in FIG. 8, the SEM image of Z/P-701 shows that distinct rhombic dodecahedral particles are observed, and nanoscale small particles are attached to the particles, and the structural morphology of the particles is similar to that of Z/P-801 in example 1. The Z/P-701 reflection loss curve was tested to be similar to that of example 1.
Comparative example 1
A metal organic framework/conducting polymer-derived nanomaterial whose preparation method differs from that of example 1 in that methanol in steps (2) and (3) is replaced with water. The method comprises the following specific steps:
(1) 4.7mL of aniline and 50mL of 2mol/L hydrochloric acid were added to a three-necked flask, and stirred in an ice-water bath for 1 hour. 11.4g of ammonium persulfate was dissolved in 25mL of deionized water and added to the three-necked flask using a dropping funnel over a period of about 30 min. The reaction was followed for 1h, taking care to maintain the temperature. And then washing and drying to obtain the conductive polyaniline.
(2) 1.1640g of cobalt nitrate hexahydrate is dissolved in 60mL of deionized water, and ultrasonic dispersion is carried out for 10 minutes; dissolving 0.0400g of polyvinylpyrrolidone in 10mL of deionized water, and performing ultrasonic dispersion for 10 minutes; the two solutions were sequentially dropped into 0.0920g of dried polyaniline, and reacted for 6 hours under magnetic stirring in a water bath at 60 ℃ to obtain a prepreg solution.
(3) 2.6272g of 2-methylimidazole was dissolved in 60mL of deionized water, and the solution was dispersed by sonication for 10 minutes, dropped into the prepreg solution, and reacted for 12 hours with continued magnetic stirring in a water bath at 60 ℃. Centrifugation and washing with methanol 3 times, the centrifuged product was collected and dried in a vacuum oven at 60 ℃ for 24 hours to obtain a black powder.
(4) Grinding the powder, putting the powder into a tube furnace filled with nitrogen for pyrolysis at 800 ℃, keeping the temperature at a rate of 2 ℃/min below 460 ℃ and 1 ℃/min above 460 ℃ for 6 hours, cooling along with the furnace, grinding, and marking the product as Z/P-809.
As shown in FIG. 9, the SEM image of Z/P-809 shows that the surface of polyaniline is not supported by rhombic dodecahedron particles. It can be seen that ZIF-67 cannot be formed in situ on polyaniline using water as a solvent.
The reflection loss curve of Z/P-809 is shown in figure 10, and it can be seen from the figure that Z/P-809 has no wave absorbing performance basically, and the reflection loss is minimum-2.46 dB.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A metal organic framework/conducting polymer derived nanomaterial characterized by: comprises a first carbon structure, a second carbon structure and a metal simple substance;
the first carbon structure has a network structure and is formed by pyrolysis of conductive polyaniline;
the second carbon structure and the metal simple substance are formed by pyrolyzing a metal organic framework, the metal simple substance is dispersed in the second carbon structure, and an integral structure formed by the second carbon structure and the metal simple substance is loaded on the first carbon structure.
2. The metal-organic framework/conducting polymer derived nanomaterial of claim 1, wherein: the metal elementary substance comprises at least one of Fe, Co, Cu, Zn and Ni.
3. The metal-organic framework/conducting polymer derived nanomaterial of claim 1, wherein: the second carbon structure has at least one of a rhombohedral structure and a cubic structure.
4. The metal-organic framework/conducting polymer derived nanomaterial of claim 1, wherein: the metal organic framework comprises at least one of ZIF-67 and ZIF-8.
5. The method for preparing the metal organic framework/conducting polymer derived nano-material as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: the method comprises the following steps:
growing a metal organic framework on the conductive polyaniline in situ to obtain a polyaniline/metal organic framework composite material; and pyrolyzing the polyaniline/metal organic framework composite material to obtain the metal organic framework/conductive polymer derived nano material.
6. The method according to claim 5, wherein: the conductive polyaniline is prepared by the following method: and in the presence of protonic acid, aniline is subjected to polymerization reaction to obtain the conductive polyaniline.
7. The method according to claim 5, wherein: the step of growing the metal organic framework in situ on the conductive polyaniline specifically comprises the following steps: in an organic solvent, mixing conductive polyaniline with a precursor of a metal organic framework, wherein the precursor of the metal organic framework forms the metal organic framework in situ on the conductive polyaniline.
8. The method according to claim 7, wherein: the precursor of the metal organic framework comprises metal salt, a surfactant and an organic ligand, wherein the ratio of metal elements in the metal salt to polyaniline is 1 mol: 10-120 g.
9. The method according to claim 5, wherein: and the temperature for pyrolyzing the polyaniline/metal organic framework composite material is 600-1000 ℃.
10. Use of the metal organic framework/conducting polymer derived nanomaterial of any of claims 1 to 4 in electromagnetic wave absorption.
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| CN115386337B (en) * | 2022-08-12 | 2023-09-08 | 许昌学院 | Chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and preparation method thereof |
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