CN112608715A - Low-dimensional structure Co/C/Fe composite wave-absorbing material prepared by taking MOFs as template and preparation method thereof - Google Patents
Low-dimensional structure Co/C/Fe composite wave-absorbing material prepared by taking MOFs as template and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a Co/C/Fe composite wave-absorbing material with a low-dimensional structure and a preparation method thereof, wherein the Co/C/Fe composite wave-absorbing material is prepared by taking MOFs as a template, and the preparation method comprises the following steps: preparing a Co/Zn bimetal MOFs template with a low-dimensional structure; adding a Co/Zn bimetal MOFs template with a low-dimensional structure into kerosene to prepare a suspension; placing the vessel containing the suspension in an oil bath, and adding Fe (CO)5Adding the suspension into an evaporator, and connecting the evaporator with a vessel filled with the suspension through a pipeline; heating the evaporator, keeping the suspension in a stirring state, and heating the oil bath pan; introducing inert gas into the evaporator, introducing Fe (CO)5Steam enters a vessel to carry out decomposition reaction so as to prepare a product A; and calcining the product A in an inert atmosphere to prepare the Co/C/Fe composite wave-absorbing material with the low-dimensional structure. According to the invention, the core-shell structure formed by coating the magnetic metal layer on the surface of the low-dimensional porous carbon material derived from MOFs (metal-organic frameworks) enhances the multiple polarization loss of the composite materialThe magnetic loss capability promotes the improvement of the electromagnetic wave absorption performance of the composite material.
Description
Technical Field
The invention belongs to the technical field of electromagnetic wave absorbing materials, and relates to a Co/C/Fe composite wave absorbing material with a low-dimensional structure and prepared by taking MOFs as a template and a preparation method thereof.
Background
The development of the radar detection technology puts higher requirements on the stealth performance of military equipment, and the development of light wave-absorbing materials with low matching thickness, wide absorption frequency band and high absorption strength has important significance on improving the stealth protection performance of the military equipment.
Carbonyl iron has good wave absorbing performance, but because the main component of the carbonyl iron is metal Fe with high density, the method for modifying the light morphology of the carbonyl iron is very limited, and the thermal decomposition method can convert Fe (CO)5The vapor is deposited on the surface of the base material after thermal decomposition, which provides a flexible synthesis process for constructing the core-shell structure wave-absorbing material by compounding carbonyl iron and other materials.
The magnetic Metal/porous carbon composite material derived from Metal Organic Frameworks (MOFs) inherits the advantages of the morphology structure, porosity, light weight and the like of the MOFs template, and has the characteristic that structural components are easy to regulate and control. On one hand, composite materials with different graphitization degrees, pore size distribution and specific surface areas can be prepared by adjusting the proportion of metal elements in the bimetallic MOFs template; on the other hand, the magnetic metal nanoparticles are uniformly distributed in the carbon skeleton of the MOFs derivatives, so that the skin effect caused by large magnetic particle particles can be effectively avoided; finally, the MOFs has good tailorability in the shape structure of the micro-nano scale, so that the derived composite material has an adjustable multi-dimensional shape structure and size, and an extremely abundant template is provided for carrying out multi-dimensional and multi-scale design and construction of the composite wave-absorbing material. Therefore, MOFs and magnetic metal/porous carbon composite materials derived from the MOFs are ideal light core particle materials for constructing a core-shell structure by compounding with carbonyl iron. The document ACS Applied Materials & Interfaces 2017,9(11): 9964-.
However, at present, the research on the preparation of the porous carbon/magnetic metal composite wave-absorbing material with the core-shell structure by taking MOFs as a template is less.
Disclosure of Invention
The invention aims to provide a Co/C/Fe composite wave-absorbing material with a low-dimensional structure and a preparation method thereof, wherein the Co/C/Fe composite wave-absorbing material is prepared by taking MOFs as a template. The Co/C/Fe composite wave-absorbing material with the low-dimensional structure prepared by the invention has relatively low density, simple and convenient preparation process, excellent wave-absorbing performance and suitability for large-scale batch production. The technical problem to be solved by the invention is realized by the following technical scheme:
the embodiment of the invention provides a preparation method of a Co/C/Fe composite wave-absorbing material with a low-dimensional structure, which is prepared by taking MOFs as a template, and comprises the following steps:
preparing a Co/Zn bimetal MOFs template with a low-dimensional structure;
adding the Co/Zn bimetal MOFs template with the low-dimensional structure into kerosene to prepare a suspension;
placing the vessel containing the suspension in an oil bath, and adding Fe (CO)5Adding the suspension into an evaporator, wherein the evaporator is connected with a vessel containing the suspension through a pipeline;
heating the evaporator, keeping the suspension in a stirring state, and heating the oil bath pan;
introducing inert gas into the evaporator, introducing Fe (CO)5Steam enters the vessel to carry out decomposition reaction so as to prepare a product A;
and calcining the product A in an inert atmosphere to prepare the Co/C/Fe composite wave-absorbing material with the low-dimensional structure.
In one embodiment of the invention, the preparation of the Co/Zn bimetal MOFs template with the low-dimensional structure comprises the following steps:
dissolving Co salt and Zn salt in deionized water to form a solution A;
dissolving dimethylimidazole and polyvinylpyrrolidone in deionized water with the same amount as the solution A to form a solution B;
and adding the solution A into the solution B to prepare the Co/Zn bimetal MOFs template with the low-dimensional structure.
In one embodiment of the invention, adding the solution A into the solution B to prepare the Co/Zn bimetal MOFs template with the low-dimensional structure comprises the following steps:
and adding the solution A into the solution B, performing magnetic stirring at room temperature, and performing suction filtration, washing and drying on a product subjected to magnetic stirring to prepare the Co/Zn bimetal MOFs template with the low-dimensional structure.
In one embodiment of the invention, the molar ratio of the Co salt to the Zn salt is any proportion, and the relationship between the number of moles of the Co salt and the Zn salt, the volume of deionized water, the dimethyl imidazole and the polyvinylpyrrolidone is 2-20 mmol: 20-100 mL: 8-80 mmol:0 or 2-20 mmol: 100-250 mL: 8-80 mmol: 0.4-0.8 g.
In one embodiment of the invention, the method for preparing the suspension by adding the Co/Zn bimetal MOFs template with the low-dimensional structure into kerosene comprises the following steps:
adding 2-5 g of the Co/Zn bimetal MOFs template with the low-dimensional structure into 100-300 mL of kerosene, and then carrying out ultrasonic dispersion for 10-30 min to prepare a suspension.
In one embodiment of the invention, the vessel containing the suspension is placed in an oil bath, and Fe (CO)5Add into the evaporimeter, and the evaporimeter passes through the tube coupling with the household utensils that contain turbid liquid, include:
adding the suspension into the vessel, and placing the vessel in the oil bath pan;
20 to 60mL of Fe (CO)5The evaporator is connected with a circulating constant-temperature water bath heating device and a vessel through a pipeline, the vessel is connected with a gas washing bottle filled with potassium permanganate solution through a condensing tube, and the evaporator is connected with an inert gas bottle through an air inlet pipe.
In one embodiment of the present invention, heating the evaporator to maintain the suspension in a stirred state while heating the oil bath includes:
heating the evaporator to 25-80 ℃;
and (3) keeping magnetic stirring of the suspension in the vessel, and heating the vessel to 180-250 ℃.
In one embodiment of the invention, inert gas is passed into the evaporator, and Fe (CO) is introduced5Steam enters the vessel to carry out decomposition reaction to prepare a product A, comprising:
introducing inert gas into the evaporator at a flow rate of 20-100 mL/min to guide Fe (CO)5Steam into the vessel to cause Fe (CO)5And (3) decomposing, reacting for 2-10 h, cooling the evaporator to room temperature under the protection of inert gas, and then carrying out suction filtration, washing and drying treatment to prepare a product A.
In one embodiment of the invention, the calcination treatment is performed on the product A under an inert atmosphere to prepare the Co/C/Fe composite wave-absorbing material with a low-dimensional structure, which comprises:
and calcining the product A at the calcining temperature of 500-900 ℃ for 1-6 h at 0.5-5 ℃/min in the nitrogen or argon atmosphere to obtain the Co/C/Fe composite wave-absorbing material with the low-dimensional structure.
According to another embodiment of the invention, the low-dimensional structure Co/C/Fe composite wave-absorbing material prepared by taking MOFs as a template is prepared by the preparation method of any one embodiment, and consists of a low-dimensional structure amorphous porous carbon skeleton inlaid with cobalt nanoparticles and carbonyl iron nanoparticles coated on the surface of the porous carbon skeleton.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the MOFs can be used for tailorably constructing the low-dimensional nuclear particles in a micro-nano-scale good morphological structure, and the magnetic metal layer is coated on the surface of the MOFs-derived low-dimensional porous carbon material to form the core-shell structure, so that the multiple polarization loss and the magnetic loss capability of the composite material are enhanced, and the improvement of the electromagnetic wave absorption performance of the composite material is promoted.
The Co/C/Fe absorbing material with the low-dimensional core-shell structure, which is prepared by the invention, has relatively low density, simple and convenient preparation process, excellent wave-absorbing performance and suitability for large-scale batch production.
Other aspects and features of the present invention will become apparent from the following detailed description, which proceeds with reference to the accompanying drawings. It is to be understood, however, that the drawings are designed solely for purposes of illustration and not as a definition of the limits of the invention, for which reference should be made to the appended claims. It should be further understood that the drawings are not necessarily drawn to scale and that, unless otherwise indicated, they are merely intended to conceptually illustrate the structures and procedures described herein.
Drawings
FIG. 1 is a flow chart of a preparation method of a Co/C/Fe composite wave-absorbing material with a low-dimensional structure prepared by taking MOFs as a template according to an embodiment of the invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of the Co/C/Fe composite wave-absorbing material with the low-dimensional structure prepared in the second and third embodiments;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the Co/C/Fe composite wave-absorbing material with the low-dimensional structure prepared in the second and third embodiments;
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of the Co/C/Fe composite wave-absorbing material with the low-dimensional structure prepared in the second and third embodiments;
FIG. 5 is a hysteresis loop of the Co/C/Fe composite wave-absorbing material with a low dimensional structure prepared in the second and third embodiments;
FIG. 6 is a graph showing the reflectivity of electromagnetic waves of the Co/C/Fe composite wave-absorbing material with a low dimensional structure prepared in example II under different thicknesses;
FIG. 7 is a graph showing the electromagnetic wave reflectivity of the Co/C/Fe composite wave-absorbing material with a low dimensional structure prepared in the third embodiment at different thicknesses;
FIG. 8 is a graph of the reflectivity of the electromagnetic waves of the Co/C/Fe composite wave-absorbing material with the low dimensional structure prepared in the fourth embodiment at different thicknesses.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example one
Referring to fig. 1, fig. 1 is a flow chart of a preparation method of a Co/C/Fe composite wave-absorbing material with a low dimensional structure prepared by using MOFs as a template according to an embodiment of the present invention. The invention provides a preparation method of a Co/C/Fe composite wave-absorbing material with a low-dimensional structure by taking MOFs as a template, which comprises the following steps:
In this embodiment, step 1 may include steps 1.1-1.3, wherein:
step 1.1, dissolving Co salt and Zn salt in deionized water to form solution A.
Specifically, 2-20 mmol of Co salt and Zn salt are dissolved in 20-250 mL of deionized water to form a solution A, wherein the total amount of the Co salt and the Zn salt is 2-20 mmol.
For example, 10mmol of Co salt and Zn salt are dissolved in 20-250 mL of deionized water to form a solution A, wherein the total amount of the Co salt and the Zn salt is 10 mmol.
Further, the molar ratio of the Co salt to the Zn salt is arbitrary.
Wherein the Co salt is Co (NO)3)2·6H2O or CoCl2·6H2O, Zn salt is Zn (NO)3)2·6H2O or ZnCl2·6H2O。
And step 1.2, dissolving dimethylimidazole and polyvinylpyrrolidone in deionized water with the same amount as the solution A to form a solution B.
Specifically, 8-80 mmol of dimethylimidazole and 0.4-0.8 mmol of polyvinylpyrrolidone (K90) are dissolved in deionized water equal to the amount of the solution A to form a solution B.
And step 1.3, adding the solution A into the solution B to prepare the Co/Zn bimetal MOFs template with the low-dimensional structure.
Specifically, the solution A is added into the solution B, magnetic stirring is carried out at room temperature (25 ℃), and then the product of the magnetic stirring is subjected to suction filtration, washing and drying treatment to prepare the Co/Zn bimetal MOFs template with the low-dimensional structure.
Namely, firstly, rapidly adding the solution A into the solution B, magnetically stirring for 2-15 hours at room temperature (25 ℃), stopping stirring after the reaction is finished, filtering out a reaction product by using a vacuum filtration method, adding a pure solvent (such as ethanol) for cleaning, filtering out the reaction product by using the vacuum filtration method, adding the pure solvent (such as ethanol) for cleaning, repeating the steps for several times (for example, 3-5 times), and drying in a drying box to prepare the Co/Zn bimetallic MOFs template with the low-dimensional structure.
Furthermore, the magnetic stirring time is 2-15 h.
Furthermore, the molar ratio of the Co salt to the Zn salt is any proportion, and the relationship between the number of moles of the Co salt and the Zn salt, the volume of deionized water, the dimethyl imidazole and the polyvinylpyrrolidone is 2-20 mmol: 20-100 mL: 8-80 mmol:0 or 2-20 mmol: 100-250 mL: 8-80 mmol: 0.4-0.8 g.
And 2, adding the Co/Zn bimetal MOFs template with the low-dimensional structure into kerosene to prepare suspension.
Specifically, 2-5 g of low-dimensional Co/Zn bimetal MOFs template is added into 100-300 mL of kerosene, and then ultrasonic dispersion is carried out for 10-30 min to prepare suspension.
Step 3, placing the vessel containing the suspension in an oil bath, and adding Fe (CO)5Adding the suspension into an evaporator, and connecting the evaporator with a vessel containing the suspension through a pipeline.
In this embodiment, step 3 may include steps 3.1-3.2, wherein:
and 3.1, adding the suspension prepared in the step 2 into a vessel, and placing the vessel into an oil bath pan.
Preferably, the vessel is a flask, for example a 250mL flask.
Step 3.2, 20-60 mL of Fe (CO)5The potassium permanganate solution is added into an evaporator, the evaporator is connected with a circulating constant-temperature water bath heating device and a vessel through a pipeline, the vessel is connected with a gas washing bottle filled with the potassium permanganate solution through a condensing tube, and the evaporator is connected with an inert gas bottle through an air inlet pipe.
Wherein, in Fe (CO)5The steam enters the vessel along with the inert gas for decomposition reactionThe gas then passes through a condenser tube into a gas scrubber containing potassium permanganate solution to prevent toxic gases from being emitted into the air.
The constant-temperature water bath heating device is used for heating the evaporator, and preferably, the model of the constant-temperature water bath heating device is HH-501.
Preferably, the evaporator is a 100mL double-jacketed reactor.
And 4, heating the evaporator, keeping the suspension in a stirring state, and heating the oil bath kettle.
In this embodiment, step 4 may include steps 4.1-4.2, where:
and 4.1, heating the evaporator to 25-80 ℃.
Specifically, the evaporator is heated to 25-80 ℃ through circulating constant-temperature water bath.
And 4.2, maintaining magnetic stirring of the suspension in the vessel, and heating the vessel to 180-250 ℃.
Specifically, magnetic stirring is carried out on the vessel in the oil bath pot by using a magnetic stirring device, and under the action of the magnetic stirring, the vessel is heated to 180-250 ℃ by using the oil bath pot.
In addition, before heating, the airtightness of the evaporator and the vessel needs to be checked, and inert gas is introduced to remove air inside the evaporator and the vessel.
Specifically, inert gas is introduced into the evaporator at a flow rate of 20-100 mL/min to guide Fe (CO)5Steam into the vessel to cause Fe (CO)5And (3) decomposing, reacting for 2-10 h, cooling the evaporator to room temperature under the protection of inert gas, and then carrying out suction filtration, washing and drying treatment to prepare a product A.
That is, after the evaporator and the oil bath are heated to a predetermined temperature, an inert gas is introduced into the evaporator at a flow rate of 20 to 100mL/min to introduce Fe (CO)5Steam into the vessel to cause Fe (CO)5Decomposing, reacting for 2-10 h, and then protecting with inert gasThen cooling to room temperature, after the reaction is finished, stopping stirring, filtering the reaction product by using a vacuum filtration method, adding a pure solvent (such as ethanol) for washing, then filtering the reaction product by using a vacuum filtration method, adding a pure solvent (such as ethanol) for washing, repeating the steps for several times, for example, 3-5 times, and then placing the reaction product into a drying oven for drying to prepare the product A.
And 6, calcining the product A in an inert atmosphere to prepare the Co/C/Fe composite wave-absorbing material with the low-dimensional structure.
Specifically, the product A is calcined for 1-6 hours at a calcination temperature of 500-900 ℃ in a nitrogen or argon atmosphere at a temperature of 0.5-5 ℃/min to obtain the low-dimensional structure Co/C/Fe composite wave-absorbing material, wherein the temperature rise speed is 0.5-5 ℃/min.
The invention firstly prepares low-dimensional MOFs nuclear particles with different components and topological structures, and then thermally decomposes Fe (CO)5Magnetic carbonyl iron particles are deposited on the surface of the composite material, and the Co/C/Fe composite material with the low-dimensional core-shell structure is prepared after high-temperature heat treatment. Fe (CO)5The carrier gas flow, the thermal decomposition temperature, the deposition time and the like in the thermal decomposition deposition process are key factors influencing the stable deposition of the carbonyl iron particles on the surfaces of the low-dimensional MOFs nuclear particles.
The Co/C/Fe composite wave-absorbing material is composed of a low-dimensional amorphous porous carbon skeleton inlaid with cobalt nanoparticles and carbonyl iron nanoparticles coated on the surface of the porous carbon skeleton, and a core-shell structure formed by magnetic coating layers enhances the multiple polarization loss and magnetic loss capacity of the composite material and promotes the improvement of the electromagnetic wave absorption performance of the composite material.
The Co/C/Fe absorbing material with the low-dimensional core-shell structure, which is prepared by the invention, has relatively low density, simple and convenient preparation process, excellent wave-absorbing performance and suitability for large-scale batch production.
It should be noted that the order of the steps of the preparation method of the present invention is not the only order for realizing the Co/C/Fe composite wave-absorbing material, and is only for convenience of describing the preparation method of this embodiment.
Example two
The embodiment provides a preparation method of a Co/C/Fe composite wave-absorbing material with a low-dimensional structure, which is prepared by taking MOFs as a template, on the basis of the first embodiment, and the preparation method comprises the following steps:
Specifically, 8mmol of Co (NO)3)2·6H2O and 2mmol Zn (NO)3)2·6H2Dissolving O in 50mL of deionized water to form a solution A, dissolving 40mmol of dimethyl imidazole in deionized water with the same quantity as the solution A to form a solution B, quickly adding the solution A into the solution B, magnetically stirring for 12 hours at room temperature (25 ℃), and carrying out suction filtration, washing and drying treatment on a generated product.
Step 3, checking the air tightness of the devices (an evaporator and a flask), introducing inert gas to remove air in the devices, heating the evaporator to 60 ℃, and heating the flask in an oil bath pot to 200 ℃ while keeping magnetic stirring; inert gas is introduced into the evaporator at a flow rate of 60mL/min, Fe (CO) is introduced5And (3) allowing steam to enter the flask for decomposition, reacting for 6 hours, cooling to room temperature under the protection of inert gas, and performing suction filtration, washing and drying treatment on a generated product.
And 4, calcining the product obtained in the step 3 in a nitrogen atmosphere at 700 ℃ at a heating rate of 1 ℃/min for 3h to obtain the Co/C/Fe composite wave-absorbing material with a sheet structure.
EXAMPLE III
The embodiment provides a preparation method of another Co/C/Fe composite wave-absorbing material with a low-dimensional structure, which is prepared by taking MOFs as a template, on the basis of the first embodiment, and the preparation method comprises the following steps:
Specifically, 8mmol of Co (NO)3)2·6H2O and 2mmol Zn (NO)3)2·6H2Dissolving O in 200mL of deionized water to form a solution A, dissolving 40mmol of dimethyl imidazole in deionized water with the same amount of 0.75g of polyvinylpyrrolidone (K90) and the solution A to form a solution B, quickly adding the solution A into the solution B, magnetically stirring for 12 hours at room temperature (25 ℃), and carrying out suction filtration, washing and drying treatment on a generated product.
Step 3, checking the air tightness of the devices (an evaporator and a flask), introducing inert gas to remove air in the devices, heating the evaporator to 60 ℃, and heating the flask in an oil bath pot to 200 ℃ while keeping magnetic stirring; inert gas is introduced into the evaporator at a flow rate of 60mL/min, Fe (CO) is introduced5And (3) allowing steam to enter the flask for decomposition, reacting for 6 hours, cooling to room temperature under the protection of inert gas, and performing suction filtration, washing and drying treatment on a generated product.
And 4, calcining the product obtained in the step 3 in a nitrogen atmosphere at 700 ℃ at a heating rate of 1 ℃/min for 3h to obtain the Co/C/Fe composite wave-absorbing material with a sheet structure.
Example four
The embodiment provides a preparation method of a Co/C/Fe composite wave-absorbing material with a low-dimensional structure, which is prepared by taking MOFs as a template, on the basis of the first embodiment, and the preparation method comprises the following steps:
Specifically, 8mmol of Co (NO)3)2·6H2O and 2mmol Zn (NO)3)2·6H2Dissolving O in 50mL of deionized water to form a solution A, dissolving 40mmol of dimethyl imidazole in deionized water with the same quantity as the solution A to form a solution B, quickly adding the solution A into the solution B, magnetically stirring for 12 hours at room temperature (25 ℃), and carrying out suction filtration, washing and drying treatment on a generated product.
Step 3, checking the air tightness of the devices (an evaporator and a flask), introducing inert gas to remove air in the devices, heating the evaporator to 60 ℃, and heating the flask in an oil bath pot to 200 ℃ while keeping magnetic stirring; inert gas is introduced into the evaporator at a flow rate of 60mL/min, Fe (CO) is introduced5And (3) allowing steam to enter the flask for decomposition, reacting for 4 hours, cooling to room temperature under the protection of inert gas, and performing suction filtration, washing and drying treatment on a generated product.
And 4, calcining the product obtained in the step 3 in a nitrogen atmosphere at the calcining temperature of 800 ℃ at the heating speed of 1 ℃/min for 3h to obtain the Co/C/Fe composite wave-absorbing material with the sheet structure.
The invention carries out XRD, SEM, static magnetic performance and electromagnetic parameter test on the final products obtained in the second, third and fourth examples.
And (3) testing results: the XRD spectrum result in figure 2 shows that the components of the low-dimensional structure Co/C/Fe composite wave-absorbing material prepared in the second and third embodiments are mainly metal Co and Fe, amorphous carbon and a small amount of graphitized carbon. FIG. 3 is a SEM morphology photograph showing that the surface of Co/C with low-dimensional MOFs diffraction can be coated with the born carbonyl iron particles uniformly. The TEM photograph shown in fig. 4 further confirms the low dimensional structure of the composite and the uniform coating of the carbonyl iron. FIG. 5 is a magnetic hysteresis loop of the Co/C/Fe composite wave-absorbing material with the low-dimensional structure prepared in the second and third embodiments at room temperature, wherein the composite material has typical ferromagnetism, and the saturation magnetization is 122.1emu/g and 182.7emu/g respectively, which shows that the product has good magnetic properties. FIGS. 6, 7 and 8 are theoretical microwave reflection loss curves of the Co/C/Fe composite wave-absorbing material with the low dimensional structure prepared in examples II, III and IV, respectively. The minimum reflectivity of the composite material prepared in the second embodiment reaches-66.30 dB (15.34GHz and 1.51mm), and the effective bandwidth (the frequency bandwidth with the reflectivity less than-10 dB) reaches 5.10GHz when the effective bandwidth is 1.54 mm; the minimum reflectivity of the composite material prepared in the third embodiment is-53.89 dB (14.92GHz and 1.71mm), and the maximum effective bandwidth reaches 5.52GHz when the thickness is 1.83 mm; the minimum reflectance of the composite prepared in example four was-51.31 dB (9.48GHz, 2.4 mm). It can be seen that the Co/C/Fe composite wave-absorbing material with the low-dimensional structure, which is prepared by taking MOFs as a template, has excellent microwave absorption performance.
EXAMPLE five
The invention also provides a low-dimensional structure Co/C/Fe composite wave-absorbing material prepared by taking MOFs as a template on the basis of the embodiments, the low-dimensional structure Co/C/Fe composite wave-absorbing material can be prepared by the preparation method provided by any one of the embodiments, and the low-dimensional structure Co/C/Fe composite wave-absorbing material is composed of a low-dimensional structure amorphous porous carbon skeleton inlaid with cobalt nanoparticles and carbonyl iron nanoparticles coated on the surface of the porous carbon skeleton.
Furthermore, the low-dimensional structure can be a one-dimensional rod or a two-dimensional sheet, the particle size of the cobalt nanoparticles is 1-50 nm, the particle size of the carbonyl iron nanoparticles is 1-300 nm, and the carbonyl iron nanoparticles are coated on the surface of the low-dimensional structure amorphous porous carbon skeleton embedded with the cobalt nanoparticles.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic data point described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples described in this specification can be combined and combined by those skilled in the art.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of a Co/C/Fe composite wave-absorbing material with a low-dimensional structure, which is prepared by taking MOFs as a template, is characterized by comprising the following steps:
preparing a Co/Zn bimetal MOFs template with a low-dimensional structure;
adding the Co/Zn bimetal MOFs template with the low-dimensional structure into kerosene to prepare a suspension;
placing the vessel containing the suspension in an oil bath, and adding Fe (CO)5Adding the suspension into an evaporator, wherein the evaporator is connected with a vessel containing the suspension through a pipeline;
heating the evaporator, keeping the suspension in a stirring state, and heating the oil bath pan;
introducing inert gas into the evaporator, introducing Fe (CO)5Steam enters the vessel to carry out decomposition reaction so as to prepare a product A;
and calcining the product A in an inert atmosphere to prepare the Co/C/Fe composite wave-absorbing material with the low-dimensional structure.
2. The preparation method according to claim 1, wherein preparing the Co/Zn bimetal MOFs template with the low dimensional structure comprises:
dissolving Co salt and Zn salt in deionized water to form a solution A;
dissolving dimethylimidazole and polyvinylpyrrolidone in deionized water with the same amount as the solution A to form a solution B;
and adding the solution A into the solution B to prepare the Co/Zn bimetal MOFs template with the low-dimensional structure.
3. The preparation method according to claim 2, wherein the solution A is added into the solution B to prepare the Co/Zn bimetal MOFs template with the low dimensional structure, and the preparation method comprises the following steps:
and adding the solution A into the solution B, performing magnetic stirring at room temperature, and performing suction filtration, washing and drying on a product subjected to magnetic stirring to prepare the Co/Zn bimetal MOFs template with the low-dimensional structure.
4. The preparation method according to claim 2 or 3, wherein the molar ratio of the Co salt to the Zn salt is any ratio, and the relationship between the number of moles of the Co salt and the Zn salt, the volume of deionized water, the dimethylimidazole and the polyvinylpyrrolidone is 2-20 mmol: 20-100 mL: 8-80 mmol:0 or 2-20 mmol: 100-250 mL: 8-80 mmol: 0.4-0.8 g.
5. The method for preparing according to claim 1, wherein adding the Co/Zn bi-metal MOFs template with low dimensional structure into kerosene to prepare a suspension comprises:
adding 2-5 g of the Co/Zn bimetal MOFs template with the low-dimensional structure into 100-300 mL of kerosene, and then carrying out ultrasonic dispersion for 10-30 min to prepare a suspension.
6. The method according to claim 1, wherein the vessel containing the suspension is placed in an oil bath, and Fe (CO) is added5Add into the evaporimeter, and the evaporimeter passes through the tube coupling with the household utensils that contain turbid liquid, include:
adding the suspension into the vessel, and placing the vessel in the oil bath pan;
20 to 60mL of Fe (CO)5The evaporator is connected with a circulating constant-temperature water bath heating device and a vessel through pipelines, and the vessel is connected with a gas washing bottle filled with potassium permanganate solution through a condensing tubeAnd the evaporator is connected with an inert gas bottle through an air inlet pipe.
7. The production method according to claim 1, wherein heating the evaporator while keeping the suspension in a stirred state and heating the oil bath pan comprises:
heating the evaporator to 25-80 ℃;
and (3) keeping magnetic stirring of the suspension in the vessel, and heating the vessel to 180-250 ℃.
8. The process according to claim 1, wherein an inert gas is introduced into the evaporator, and Fe (CO) is introduced5Steam enters the vessel to carry out decomposition reaction to prepare a product A, comprising:
introducing inert gas into the evaporator at a flow rate of 20-100 mL/min to guide Fe (CO)5Steam into the vessel to cause Fe (CO)5And (3) decomposing, reacting for 2-10 h, cooling the evaporator to room temperature under the protection of inert gas, and then carrying out suction filtration, washing and drying treatment to prepare a product A.
9. The preparation method of claim 1, wherein the product A is calcined in an inert atmosphere to prepare the Co/C/Fe composite wave-absorbing material with a low dimensional structure, and the preparation method comprises the following steps:
and calcining the product A at the calcining temperature of 500-900 ℃ for 1-6 h at the heating speed of 0.5-5 ℃/min in the nitrogen or argon atmosphere to obtain the Co/C/Fe composite wave-absorbing material with the low-dimensional structure.
10. The Co/C/Fe composite wave-absorbing material with the low-dimensional structure is prepared by the preparation method of any one of claims 1-9, and consists of a low-dimensional amorphous porous carbon skeleton inlaid with cobalt nanoparticles and carbonyl iron nanoparticles coated on the surface of the porous carbon skeleton.
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