CN114212771A - CNTs/Fe3O4Melamine composite carbon foam and preparation method and application thereof - Google Patents
CNTs/Fe3O4Melamine composite carbon foam and preparation method and application thereof Download PDFInfo
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- CN114212771A CN114212771A CN202210014981.XA CN202210014981A CN114212771A CN 114212771 A CN114212771 A CN 114212771A CN 202210014981 A CN202210014981 A CN 202210014981A CN 114212771 A CN114212771 A CN 114212771A
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- 239000002131 composite material Substances 0.000 title claims abstract description 128
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 170
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0075—Magnetic shielding materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Organic Chemistry (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a CNTs/Fe3O4Melamine composite carbon foam and a preparation method and application thereof. The preparation method comprises the steps of preparing a flexible carbon matrix material by using melamine sponge as a raw material through a carbonization process and an in-situ growth carbon nanotube process in sequence, then growing an iron-based MOFs crystal material on the surface of the carbon matrix material in situ to obtain a CNTs/Fe-MOFs/melamine composite material, and performing carbonization treatment to obtain the flexible CNTs/Fe3O4Melamine composite carbon foam. The composite carbon foam prepared by the method realizes Fe3O4The high dispersion of the nano-particles is beneficial to improving the electromagnetic shielding performance of the composite foam carbon. The material shows excellent electromagnetic shielding performance when being used in the field of electromagnetic shielding.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to CNTs/Fe3O4Melamine composite carbon foam, a preparation method thereof and application thereof in electromagnetic shielding.
Background
With the wide application of modern electronic products and the indiscriminate coverage of wireless transmission signals, electromagnetic waves are used as basic carriers for information propagation and exist in the living space of people. Meanwhile, no matter the electronic components used by the electronic products or various signal towers inevitably generate electromagnetic pollution, and the electromagnetic pollution can shorten the service life of the electronic equipment and have certain influence on the sensitivity performance of the electronic equipment. Since electromagnetic shielding is one of means capable of effectively controlling the problems of electromagnetic interference and pollution, applying a certain amount of electromagnetic shielding to various electronic products is an optimal solution for preventing adverse effects of electromagnetic pollution on human health and the surrounding environment, and thus, researches on electromagnetic shielding materials are receiving increasing attention.
Because the traditional metal electromagnetic shielding material has the defects of high density, high corrosion tendency, high processing difficulty and the like, and the matching degree of small and miniature equipment is low, the electromagnetic shielding material used for replacing the metal material is widely concerned, wherein the carbon-based material has large specific surface area, good conductivity, easy regulation and control of structure, low density, stable chemical property, high temperature resistance and the like, so that the relevant research of the carbon-based electromagnetic shielding material is rapidly developed. The carbon material and metal or metal oxide are compounded to hopefully prepare the novel electromagnetic shielding material integrating light weight, thinness and high electromagnetic shielding performance.
The ferrite is used as a shielding filler, the main principle of shielding electromagnetic waves is the combined action of dielectric loss and magnetic loss, and the ferrite has high conductivity and good permeability in a plurality of frequency band ranges, so that the electromagnetic waves are quickly attenuated after entering a shielding body. As a typical representative of ferrite, Fe3O4Is a typical ferrite with a trans-spinel structure, has outstanding performances in both magnetic loss and dielectric loss, and Fe3O4Also has the advantages of unique surface effect and the like, and is widely applied as shielding filler. The method is characterized in that divalent and trivalent ferric salts are mixed, and the coprecipitation method is adopted to prepare the nano Fe3O4Particles of nano Fe3O4Particle-based method, but the Fe obtained by this method3O4The particles have the disadvantage of being prone to agglomeration, and thus how to increase Fe3O4The particle dispersion property becomes a key issue to improve its electromagnetic shielding property.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
According to the inventionOne purpose is to provide a CNTs/Fe3O4Melamine composite carbon foam, Fe3O4The nano particles are highly dispersed on the surface of the carbon matrix.
Another object of the present invention is to provide the above-mentioned CNTs/Fe3O4The preparation method of the melamine composite carbon foam comprises the steps of growing the Fe-MOFs material with the nanometer level particles on the surface of a carbon substrate in situ by a specific method, and realizing Fe after carbonization3O4High dispersion of nanoparticles.
Another object of the present invention is to provide an electromagnetic shielding composition comprising the above-mentioned CNTs/Fe3O4Melamine composite carbon foam or CNTs/Fe prepared by the preparation method3O4Melamine composite carbon foam.
The fourth object of the present invention is to provide the above-mentioned CNTs/Fe3O4Melamine composite carbon foam or CNTs/Fe prepared by the preparation method3O4The melamine composite carbon foam shows excellent electromagnetic shielding performance when applied to electromagnetic shielding.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in one aspect, the invention provides a CNTs/Fe3O4Melamine composite carbon foam comprising:
the CNTs/melamine composite carbon base material is composed of a melamine carbon foam framework and carbon nanotubes loaded on the melamine carbon foam framework;
and, Fe3O4The nano particles are dispersed on the CNTs/melamine composite carbon base material;
the source of the melamine carbon foam is not particularly limited and may be commercially available or prepared according to methods and conditions known in the art. In some embodiments, the melamine carbon foam is obtained by carbonizing a melamine sponge.
The method of forming the carbon nanotubes supported is not particularly limited, and the carbon nanotubes may be supported on the melamine carbon foam according to a method known in the art. In some embodiments, the carbon nanotubes are deposited and grown on the melamine carbon foam by using a chemical vapor deposition method, so that the carbon nanotube loading is realized.
In some embodiments, the loading amount of the carbon nanotubes on the CNTs/melamine composite carbon matrix material is 1-8 mg/cm3(e.g., 1.6, 2.2, 3.2, 4.0, 4.9, 6.3mg/cm3)。
Fe of the invention3O4The nanoparticles are highly dispersed on the surface of the CNTs/melamine composite carbon matrix material, and in some embodiments, Fe3O4The nanoparticles have a particle size of 10 to 200nm, preferably 18 to 160nm, more preferably 15 to 50nm, for example 18.85 to 43.73 nm.
In some embodiments, highly dispersed Fe3O4The nano particles are obtained by growing a Fe-MOFs material with nano-grade particles on the surface of a CNTs/melamine composite carbon matrix material in situ and then carbonizing the Fe-MOFs material.
Further, in some embodiments, Fe3O4Nanoparticles in CNTs/Fe3O4The load capacity of the melamine composite carbon foam is 0.1-20 mg/cm3。
The amount of the supported catalyst is a unit volume (cm)3)CNTs/Fe3O4Fe in melamine composite carbon foam3O4Weight of nanoparticles (mg), i.e. Fe3O4Weight of nanoparticles (mg)/(CNTs/Fe)3O4Volume of melamine composite carbon foam) (cm3)。
On the other hand, the invention provides a method for preparing CNTs/Fe3O4A method for preparing melamine composite carbon foam comprises the following steps:
(1) obtaining melamine carbon foam;
(2) depositing and growing carbon nanotubes on the melamine carbon foam to obtain a CNTs/melamine composite carbon matrix material;
(3) adding iron salt, an organic ligand and an additive into a methanol solvent or a mixed solvent of N, N-dimethylformamide and methanol to obtain a mixed solution, immersing the CNTs/melamine composite carbon base material into the mixed solution, and putting the CNTs/melamine composite carbon base material into a reaction kettle for reaction, so that a nano-grade granular Fe-MOFs material grows in situ on the CNTs/melamine composite carbon base material, and thus CNTs/Fe-MOFs/melamine composite carbon foam is obtained;
(4) carbonizing the CNTs/Fe-MOFs/melamine composite carbon foam to obtain CNTs/Fe3O4Melamine composite carbon foam.
Step (1)
The source of the melamine carbon foam is not particularly limited and may be commercially available or prepared according to methods and conditions known in the art.
In some embodiments, step (1) comprises: carbonizing melamine sponge to obtain melamine carbon foam;
the size and shape of the melamine sponge are not particularly limited, and the melamine sponge having a corresponding size and shape can be obtained by purchasing or selecting an appropriate method and conditions according to the size required in the field of application or can be cut into pieces. In some embodiments, the melamine sponge may be in the shape of a cuboid and may be in the dimensions of 90mm long, 28mm wide and 20mm high, but is not limited thereto.
The carbonization conditions are not particularly limited, and any conditions capable of carbonizing to form carbon foam in the art may be employed. In some embodiments, the carbonization temperature is 700 to 900 ℃ (e.g., 700, 800, 900 ℃) and the carbonization time is 1 to 3 hours (e.g., 1,2, 3 hours).
In one embodiment, step (1) comprises:
cutting a commercial melamine sponge into cuboids with the length, width and thickness of 90mm, 28mm and 20mm respectively for later use; soaking the cut sample in an ethanol solution, ultrasonically oscillating for 30min, repeatedly cleaning for three times, and washing off attached impurities for later use; the pre-washed melamine sponge was placed in a quartz dish and then moved into a tube furnace under high purity N2Under the protection of (2 ℃), the temperature is raised to 700-900 ℃ at the heating rate of 2 ℃/min, and then the carbonization is carried out in a tubular furnace at the constant temperature for 2hA process; and after the reaction is finished, waiting for the tubular furnace to be naturally cooled to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using an ethanol solution, and drying to obtain the melamine-based carbon foam.
Step (2)
The manner of depositing the growing carbon nanotubes is not particularly limited and the growing carbon nanotubes can be deposited on the melamine carbon foam according to methods known in the art. In some embodiments, growing carbon nanotubes are deposited on the melamine carbon foam using chemical vapor deposition;
further, in some embodiments, step (2) comprises:
heating melamine carbon foam in an inert environment, introducing a ferrocene toluene solution, and depositing and growing a carbon nano tube on the melamine carbon foam through chemical vapor deposition;
the temperature of the elevated temperature is not particularly limited, and any temperature suitable for chemical vapor deposition in the art may be employed. In some embodiments, the elevated temperature is 700-900 ℃ (e.g., 700, 800, 900 ℃);
the concentration of ferrocene is not particularly limited and any concentration suitable for forming carbon nanotubes in the art may be used. In some embodiments, the concentration of ferrocene in the toluene solution of ferrocene is 3 to 5 wt% (e.g., 4 wt%).
In one embodiment, step (2) comprises:
weighing ferrocene in advance by using an analytical balance, dissolving the ferrocene in toluene to prepare 4 wt% of ferrocene-toluene mixed solution, and fully and uniformly mixing the ferrocene and the toluene, and then placing the mixture at normal temperature for later use.
Placing the prepared melamine-based carbon foam above an iron wire tray and moving the melamine-based carbon foam into a tubular furnace, and reacting the melamine-based carbon foam with high-purity N2Under the protection of (2), the temperature is raised to 800 ℃ at a temperature rise rate of 4 ℃/min. At this time, the flow of the protective gas was reduced and the prepared ferrocene-toluene mixed solution was introduced into the furnace at a rate of 0.45ml/min so that N was present2Carrying mixed steam of ferrocene and toluene, flowing through the whole tube furnace, and growing Carbon Nanotubes (CNTs) by Chemical Vapor Deposition (CVD) at a constant temperature for 3 h.
In the obtained CNTs/melamine composite carbon base material, the loading capacity of the carbon nano tubes on the CNTs/melamine composite carbon base material is 1-8 mg/cm3。
Step (3)
In the step, nano-grade granular Fe-MOFs (crystalline Fe-MOFs) materials are grown in situ on the CNTs/melamine composite carbon base materials, and high-dispersion Fe can be formed through subsequent carbonization3O4And (3) nanoparticles.
The iron salt may be a precursor known in the art for synthesizing Fe metal parts of Fe-MOFs materials, including but not limited to ferric trichloride hexahydrate, ferric acetate, ferric nitrate, ferric sulfate, and the like.
The organic ligand may be an organic ligand known in the art to act as a bridging between the MOFs material and the Fe metal moiety, including but not limited to terephthalic acid, trimesic acid, 1,2, 4-triazole, and the like.
The additive may be a substance added during the synthesis of the MOFs material known in the art, including but not limited to trifluoroacetic acid, trifluoromethanesulfonic acid, and the like.
In the step, methanol or a mixture of N, N-dimethylformamide and methanol is selected as a solvent in the process of synthesizing MOFs materials, so that the structural morphology of the MOFs materials is regulated and controlled, crystalline MOFs are formed, the MOF crystals are promoted to generate structural defects, and the solvent not only serves as a guest molecule in the MOF synthesis process, but also has a significant influence on the structure of the MOF materials. For example, two MOF-5 cuboids synthesized under different solvent systems, a N, N-Dimethylformamide (DMF) solution can form dense MOF crystals, and a N, N-Diethylformamide (DEF) solution can form mesomorphic MOF cuboids, indicating that the solvent has a large influence on the surface morphology and internal structure of the MOF-5 cuboids and can generate structural defects in the MOF crystals.
In some embodiments, the volume ratio of N, N-dimethylformamide to methanol is 0 to 1, for example, the volume ratio of N, N-dimethylformamide to methanol may be 1:4, 2:3, or 1:1, but not limited thereto. When the volume ratio is 0, it means that methanol alone is used as a solvent.
In some embodiments, the reaction temperature is 150 ℃ and the reaction time is 24 h.
In one embodiment, step (3) comprises:
adding ferric trichloride hexahydrate, terephthalic acid, 1,2, 4-triazole and trifluoroacetic acid into a mixed solvent of N, N-dimethylformamide and methanol (N, N-dimethylformamide: methanol (v/v): 0-1) in proportion, stirring at normal temperature for three hours, immersing the CNTs/melamine composite carbon foam into the mixed solution, putting the CNTs/melamine composite carbon foam into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene, reacting at 150 ℃ for 24 hours, naturally cooling, washing a reaction product with the N, N-dimethylformamide and absolute ethyl alcohol, performing suction filtration and drying to obtain the CNTs/Fe-MOFs/melamine composite carbon foam material.
Step (4)
The carbonization conditions are not particularly limited, and any material capable of carbonizing Fe-MOFs to form C and Fe in the art may be used3O4The conditions of (1). In some embodiments, the carbonization temperature is 500 to 600 ℃ (e.g., 500, 550, 600 ℃) and the carbonization time is 1 to 3 hours (e.g., 1,2, 3 hours).
In one embodiment, step (4) comprises:
placing the CNTs/Fe-MOFs/melamine composite carbon foam material into a quartz tube in a ceramic boat, then heating to 550 ℃ under the condition of 5 ℃/min in an argon atmosphere in a tube furnace, and preserving heat for 2h to obtain the CNTs/Fe3O4The melamine composite carbon foam material is black solid powder.
By comparing CNTs/Fe3O4The weight difference between the melamine composite carbon foam and the CNTs/melamine can obtain Fe3O4Is divided by CNTs/Fe3O4Volume of melamine composite carbon foam to obtain corresponding Fe3O4The amount of the supported.
The obtained CNTs/Fe3O4In the melamine composite carbon foam, Fe3O4Nanoparticles in CNTs/Fe3O4The load capacity of the melamine composite carbon foam is 0.1-20 mg/cm3。
The amount of the supported catalyst is a unit volume (cm)3)CNTs/Fe3O4Fe in melamine composite carbon foam3O4Weight of nanoparticles (mg), i.e. Fe3O4Weight of nanoparticles (mg)/(CNTs/Fe)3O4Volume (cm) of/Melamine) composite carbon foam3)。
In another aspect, the present invention provides an electromagnetic shielding composition comprising the CNTs/Fe3O4Melamine composite carbon foam or CNTs/Fe prepared by the preparation method3O4Melamine composite carbon foam.
The electromagnetic shielding composition can be, for example, a composite electromagnetic shielding material prepared by adding graphene, a composite electromagnetic shielding material prepared by adding carbon nanotubes, and a composite electromagnetic shielding material prepared by adding ferrite. The electromagnetic shielding composition may also contain additives, such as Fe, depending on the particular application3O4Graphene, nanotube, alpha-Fe2O3。
In another aspect, the invention provides a CNTs/Fe as described above3O4Melamine composite carbon foam or CNTs/Fe prepared by the preparation method3O4The melamine composite carbon foam is applied to electromagnetic shielding.
The electromagnetic shielding performance test method comprises the following steps:
the samples were cut into 10.1X 22.8X 3.0mm blocks and the reflectance of solid material, i.e.the S parameter (S), of the melamine-based carbon foam samples was determined by means of an Agilent vector network analyzer, model No. N5234A11，S21) Detection is performed and the transmission power is set to-5 dB. And calculating electromagnetic shielding parameters. The specific calculation formula is as follows:
SET＝SER+SEA (1)
SER＝-10log10(1-R) (2)
SEA＝-10log10[T/(1-R)] (3)
R＝10(S11/10) (4)
T＝10(S21/10) (5)
A＝1-R-T
wherein: SET-total electromagnetic shielding performance, dB;
SERmaterial surface reflection loss, dB;
SEA-material internal absorption loss, dB;
r-material reflectance (%);
a-material absorption (%);
t-material transmittance (%);
CNTs/Fe of the invention3O4Total electromagnetic shielding performance SE of melamine composite carbon foamTCan reach 35-47 dB, and is a light, thin, soft and high-performance electromagnetic shielding material.
The technical scheme of the invention has the following beneficial effects:
(1) the invention adopts Melamine (Melamine) sponge to directly carbonize to prepare Melamine-based carbon foam, loads Carbon Nano Tubes (CNTs) on a carbon structure framework of the Melamine-based carbon foam, obtains the CNTs/Fe-MOFs/Melamine composite material through in-situ growth of a metal Fe organic framework material (Fe-MOFs) on the CNTs/Melamine composite carbon matrix material, and finally obtains Fe through further carbonization treatment3O4CNTs/Fe with nano particles highly dispersed on surface of carbon matrix3O4A melamine composite. Electromagnetic shielding performance tests show that the material is a light, thin, soft and high-performance electromagnetic shielding material.
(2) In the synthesis process, the crystalline Fe-MOFs is formed by regulating and controlling the MOFs material, and C and Fe are exactly generated after further carbonization3O4Realize Fe3O4High dispersion of nanoparticles.
The present invention has been described in detail hereinabove, but the above embodiments are merely illustrative in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary or the following examples.
Unless expressly stated otherwise, a numerical range throughout this specification includes any sub-range therein and any numerical value incremented by the smallest sub-unit within a given value. Unless expressly stated otherwise, numerical values throughout this specification represent approximate measures or limitations to the extent that such deviations from the given values, as well as embodiments having approximately the stated values and having the exact values stated, are included. Other than in the operating examples provided at the end of the detailed description, all numbers expressing quantities or conditions of parameters (e.g., quantities or conditions) used in the specification (including the appended claims) are to be understood as being modified in all instances by the term "about" whether or not "about" actually appears before the number. "about" means that the numerical value so stated is allowed to be somewhat imprecise (with some approach to exactness in that value; about or reasonably close to that value; approximately). As used herein, "about" refers to at least variations that can be produced by ordinary methods of measuring and using such parameters, provided that the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" can include variations of less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5%.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of CNTs/melamine composite carbon foam according to example 2 of the present invention, wherein a is a low-magnification SEM image of CNTs/melamine composite carbon foam, b is a high-magnification SEM image of CNTs/melamine composite carbon foam, and c is a surface-supported carbon nanotube SEM image of CNTs/melamine composite carbon foam;
FIG. 2 is a Scanning Electron Microscope (SEM) image of Fe-MOFs materials prepared under different DMF and methanol ratios according to the present invention, wherein a is the SEM image of Fe-MOFs materials prepared under the DMF and methanol ratio of example 3, b is the SEM image of Fe-MOFs materials prepared under the DMF and methanol ratio of example 2, c is the SEM image of Fe-MOFs materials prepared under the DMF and methanol ratio of example 1, and d is the SEM image of Fe-MOFs materials prepared under the DMF and methanol ratio of example 4;
FIG. 3 is an XRD diagram of CNTs/Fe-MOFs/melamine composite carbon foam materials prepared by different DMF and methanol ratios of the invention;
FIG. 4 shows CNTs/Fe prepared in example 4 of the present invention3O4XRD pattern of/melamine composite carbon foam;
FIG. 5 shows CNTs/Fe prepared in example 4 of the present invention3O4EDS energy spectrum of melamine composite carbon foam, wherein a is CNTs/Fe3O4SEM pictures of the melamine composite carbon foam, wherein b is a corresponding Fe element distribution diagram, and c is a corresponding O element distribution diagram;
FIG. 6 shows the synthesis of CNTs/Fe from example 4 (methanol)3O4A TEM image of the melamine composite carbon foam, wherein a and b are low-magnification TEM images, and c is a high-magnification TEM image;
FIG. 7 shows CNTs/Fe prepared in examples of the present invention and comparative examples3O4Total electromagnetic shielding performance (SE) of melamine composite carbon foam in X wave bandT)；
FIG. 8 shows different Fe3O4CNTs/Fe of supported amount3O4Electromagnetic shielding average value SE of melamine composite carbon foam in X wave bandT、SEA、SER；
FIG. 9 shows CNTs/Fe prepared in example 4 of the present invention3O4Melamine composite carbon foam and Fe prepared in comparative example 23O4Residual shielding performance of melamine material after 0-50 compression cycles.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention.
Except for special instructions, raw materials, reagents, methods and the like adopted in the examples are conventional raw materials, reagents and methods in the field, except for melamine sea, the rest medicines are from Mecline reagent, and the melamine sponge is purchased from Shanghai Beiyou building materials Co., Ltd;
TEM uses JEM-2100 from JEOL, Japan, using a field emission SU-70 microscope to acquire Scanning Electron Microscopy (SEM) and energy spectroscopy (EDS) data, and XRD measurements were obtained using a Bruker D8 advanced diffractometer.
Example 1
CNTs/Fe3O4The preparation method of the melamine composite carbon foam comprises the following steps:
1. the melamine sponge is cut into cuboids with the length, width and thickness of 90mm, 28mm and 20mm respectively for later use. And soaking the cut sample in an ethanol solution, ultrasonically oscillating for 30min, repeatedly cleaning for three times, and washing away the attached impurities for later use. The pre-washed melamine sponge was placed in a quartz dish and then moved into a tube furnace under high purity N2Under the protection of (2 ℃), the temperature rises to 700 ℃ at the heating rate of 2 ℃/min, and then the carbonization process is carried out in a tubular furnace at the constant temperature for 2 h. And after the reaction is finished, waiting for the tubular furnace to be naturally cooled to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using an ethanol solution, and drying to obtain the melamine-based carbon foam.
2. Weighing ferrocene in advance by using an analytical balance, dissolving the ferrocene in toluene to prepare 4 wt% of ferrocene-toluene mixed solution, and fully and uniformly mixing the ferrocene and the toluene, and then placing the mixture at normal temperature for later use.
Placing the prepared melamine-based carbon foam above an iron wire tray and moving the melamine-based carbon foam into a tubular furnace, and reacting the melamine-based carbon foam with high-purity N2Under the protection of (2), the temperature is raised to 800 ℃ at a temperature rise rate of 4 ℃/min. At this time, the flow of the protective gas was reduced and the prepared ferrocene-toluene mixed solution was introduced into the furnace at a rate of 0.45ml/min so that N was present2Carrying mixed steam of ferrocene and toluene, flowing through the whole tube furnace, and growing Carbon Nanotubes (CNTs) by Chemical Vapor Deposition (CVD) at a constant temperature for 3 h.
3. 0.4113g of ferric trichloride hexahydrate, 0.1495g of terephthalic acid, 0.065g of 1,2, 4-triazole and 195.4 mu l of trifluoroacetic acid are added into a mixed solvent of 0.632ml of N, N-dimethylformamide and 2.528ml of methanol (N, N-dimethylformamide: 1/4), the mixture is stirred for three hours at normal temperature, CNTs/melamine composite carbon foam is immersed into the mixed solution, the CNTs/melamine composite carbon foam and the mixed solution are placed into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene, the reaction is carried out for 24 hours at 150 ℃, then the reaction product is naturally cooled, the reaction product is cleaned by N, N-dimethylformamide and absolute ethyl alcohol, the CNTs/Fe-MOFs/melamine composite carbon foam material is obtained by suction filtration and drying, and an XRD (X-ray diffraction) diagram is shown in figure 3.
By comparing the XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOF, the growth of the Fe-MOF material is not influenced by the addition of the CNTs/melamine composite carbon foam.
The Fe-MOFs material does not include step 1 and step 2, and the Fe-MOFs material is obtained by directly adopting step 3, and the XRD pattern of the Fe-MOFs material is shown as c in figure 2.
4. Weighing a certain amount of CNTs/Fe-MOFs/melamine composite carbon foam material in a ceramic boat, putting the ceramic boat in a quartz tube, heating to 550 ℃ under the condition of 5 ℃/min in an argon atmosphere in a tube furnace, and preserving heat for 2h to obtain the CNTs/Fe3O4The melamine composite carbon foam is black solid powder.
Example 2
CNTs/Fe3O4The preparation method of the melamine composite carbon foam comprises the following steps:
1. the melamine sponge is cut into cuboids with the length, width and thickness of 90mm, 28mm and 20mm respectively for later use. And soaking the cut sample in an ethanol solution, ultrasonically oscillating for 30min, repeatedly cleaning for three times, and washing away the attached impurities for later use. The pre-washed melamine sponge was placed in a quartz dish and then moved into a tube furnace under high purity N2Under the protection of (2 ℃), the temperature is raised to 800 ℃ at the heating rate of 2 ℃/min, and then the carbonization process is carried out in a tubular furnace at the constant temperature for 2 h. And after the reaction is finished, waiting for the tubular furnace to be naturally cooled to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using an ethanol solution, and drying to obtain the melamine-based carbon foam.
2. Weighing ferrocene in advance by using an analytical balance, dissolving the ferrocene in toluene to prepare 4 wt% of ferrocene-toluene mixed solution, and fully and uniformly mixing the ferrocene and the toluene, and then placing the mixture at normal temperature for later use.
Placing the prepared melamine-based carbon foam in a containerMoving the iron wire tray into a tube furnace above the iron wire tray, and placing the iron wire tray in a high-purity N furnace2Under the protection of (2), the temperature is raised to 800 ℃ at a temperature rise rate of 4 ℃/min. At this time, the flow of the protective gas was reduced and the prepared ferrocene-toluene mixed solution was introduced into the furnace at a rate of 0.45ml/min so that N was present2The mixed vapor carrying ferrocene and toluene flows through the whole tube furnace, and Carbon Nanotubes (CNTs) are grown by Chemical Vapor Deposition (CVD) at a constant temperature for 3h, and the obtained CNTs/melamine composite carbon foam SEM is shown in FIG. 1, wherein the carbon nanotubes are hollow.
3. 0.4113g of ferric trichloride hexahydrate, 0.1495g of terephthalic acid, 0.065g of 1,2, 4-triazole and 195.4 mu l of trifluoroacetic acid are added into a mixed solvent of 1.264ml of N, N-dimethylformamide and 1.896ml of methanol (N, N-dimethylformamide: 2/3), the mixture is stirred for three hours at normal temperature, CNTs/melamine composite carbon foam is immersed into the mixed solution, the CNTs/melamine composite carbon foam and the mixed solution are placed into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene, the reaction is carried out for 24 hours at 150 ℃, then the reaction product is naturally cooled, the reaction product is cleaned by N, N-dimethylformamide and absolute ethyl alcohol, the CNTs/Fe-MOFs/melamine composite carbon foam material is obtained by suction filtration and drying, and an XRD (X-ray diffraction) diagram is shown in figure 3.
The Fe-MOFs material does not include step 1 and step 2, and the Fe-MOFs material is obtained by directly adopting step 3, and the XRD pattern of the Fe-MOFs material is shown as b in figure 2.
By comparing the XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOF, the growth of the Fe-MOF material is not influenced by the addition of the CNTs/melamine composite carbon foam.
4. Weighing a certain amount of CNTs/Fe-MOFs/melamine composite carbon foam material in a ceramic boat, putting the ceramic boat in a quartz tube, heating to 550 ℃ under the condition of 5 ℃/min in an argon atmosphere in a tube furnace, and preserving heat for 2h to obtain the CNTs/Fe3O4The melamine composite carbon foam is black solid powder.
Example 3
CNTs/Fe3O4The preparation method of the melamine composite carbon foam comprises the following steps:
1. cutting Melamine sponge into length, width and thicknessThe cuboids are respectively 90mm, 28mm and 20mm for standby. And soaking the cut sample in an ethanol solution, ultrasonically oscillating for 30min, repeatedly cleaning for three times, and washing away the attached impurities for later use. The pre-washed melamine sponge was placed in a quartz dish and then moved into a tube furnace under high purity N2Under the protection of (2 ℃), the temperature rises to 850 ℃ at the heating rate of 2 ℃/min, and then the carbonization process is carried out in a tubular furnace at the constant temperature for 2 h. And after the reaction is finished, waiting for the tubular furnace to be naturally cooled to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using an ethanol solution, and drying to obtain the melamine-based carbon foam.
2. Weighing ferrocene in advance by using an analytical balance, dissolving the ferrocene in toluene to prepare 4 wt% of ferrocene-toluene mixed solution, and fully and uniformly mixing the ferrocene and the toluene, and then placing the mixture at normal temperature for later use.
Placing the prepared melamine-based carbon foam above an iron wire tray and moving the melamine-based carbon foam into a tubular furnace, and reacting the melamine-based carbon foam with high-purity N2Under the protection of (2), the temperature is raised to 800 ℃ at a temperature rise rate of 4 ℃/min. At this time, the flow of the protective gas was reduced and the prepared ferrocene-toluene mixed solution was introduced into the furnace at a rate of 0.45ml/min so that N was present2Carrying mixed steam of ferrocene and toluene, flowing through the whole tube furnace, and growing Carbon Nanotubes (CNTs) by Chemical Vapor Deposition (CVD) at a constant temperature for 3 h.
3. 0.4113g of ferric trichloride hexahydrate, 0.1495g of terephthalic acid, 0.065g of 1,2, 4-triazole and 195.4 mu l of trifluoroacetic acid are added into a mixed solvent of 1.58ml of N, N-dimethylformamide and 1.58ml of methanol (N, N-dimethylformamide: methanol: 1/1), the mixture is stirred for three hours at normal temperature, CNTs/melamine composite carbon foam is immersed into the mixed solution, the CNTs/melamine composite carbon foam and the mixed solution are placed into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene together, the reaction is carried out for 24 hours at 150 ℃, then the reaction product is naturally cooled, the reaction product is cleaned by the N, N-dimethylformamide and absolute ethyl alcohol, the CNTs/Fe-MOFs/melamine composite carbon foam material is obtained by suction filtration and drying, and an XRD (X-ray diffraction) diagram is shown in figure 3.
By comparing the XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOFs, the growth of the Fe-MOF material is not influenced by the addition of the CNTs/melamine composite carbon foam.
The Fe-MOFs material does not include step 1 and step 2, and the Fe-MOFs material is obtained by directly adopting step 3, and the XRD pattern of the Fe-MOFs material is shown as a in figure 2.
4. Weighing a certain amount of CNTs/Fe-MOFs/melamine composite carbon foam material in a ceramic boat, putting the ceramic boat in a quartz tube, heating to 550 ℃ under the condition of 5 ℃/min in an argon atmosphere in a tube furnace, and preserving heat for 2h to obtain the CNTs/Fe3O4The melamine composite carbon foam is black solid powder.
Example 4
CNTs/Fe3O4The preparation method of the melamine composite carbon foam comprises the following steps:
1. the melamine sponge is cut into cuboids with the length, width and thickness of 90mm, 28mm and 20mm respectively for later use. And soaking the cut sample in an ethanol solution, ultrasonically oscillating for 30min, repeatedly cleaning for three times, and washing away the attached impurities for later use. The pre-washed melamine sponge was placed in a quartz dish and then moved into a tube furnace under high purity N2Under the protection of (2 ℃), the temperature is increased to 900 ℃ at the heating rate of 2 ℃/min, and then the carbonization process is carried out in a tubular furnace at the constant temperature for 2 h. And after the reaction is finished, waiting for the tubular furnace to be naturally cooled to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using an ethanol solution, and drying to obtain the melamine-based carbon foam.
2. Weighing ferrocene in advance by using an analytical balance, dissolving the ferrocene in toluene to prepare 4 wt% of ferrocene-toluene mixed solution, and fully and uniformly mixing the ferrocene and the toluene, and then placing the mixture at normal temperature for later use.
Placing the prepared melamine-based carbon foam above an iron wire tray and moving the melamine-based carbon foam into a tubular furnace, and reacting the melamine-based carbon foam with high-purity N2Under the protection of (2), the temperature is raised to 800 ℃ at a temperature rise rate of 4 ℃/min. At this time, the flow of the protective gas was reduced and the prepared ferrocene-toluene mixed solution was introduced into the furnace at a rate of 0.45ml/min so that N was present2Carrying mixed steam of ferrocene and toluene, flowing through the whole tube furnace, and growing Carbon Nanotubes (CNTs) by Chemical Vapor Deposition (CVD) at a constant temperature for 3 h.
3. 0.4113g of ferric trichloride hexahydrate, 0.1495g of terephthalic acid, 0.065g of 1,2, 4-triazole and 195.4 mu l of trifluoroacetic acid are added into 3.16ml of methanol (equivalent to N, N-dimethylformamide: methanol ═ 0), the mixture is stirred for three hours at normal temperature, the CNTs/melamine composite carbon foam is immersed into the mixed solution, the CNTs/melamine composite carbon foam and the mixed solution are put into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene, the reaction kettle is naturally cooled after reacting for 24 hours at 150 ℃, reaction products are cleaned by the N, N-dimethylformamide and absolute ethyl alcohol, and the CNTs/Fe-MOFs/melamine composite carbon foam is obtained after suction filtration and drying, wherein an XRD (X-ray diffraction) diagram is shown in figure 3.
By comparing XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOFs material, the growth of the Fe-MOF material is not influenced by the addition of the CNTs/melamine composite carbon foam.
The Fe-MOFs material does not include step 1 and step 2, and the Fe-MOFs material is obtained by directly adopting step 3, and the XRD pattern of the Fe-MOFs material is shown as d in figure 2.
4. Weighing a certain amount of CNTs/Fe-MOFs/melamine composite carbon foam material in a ceramic boat, putting the ceramic boat in a quartz tube, heating to 550 ℃ under the condition of 5 ℃/min in an argon atmosphere in a tube furnace, and preserving heat for 2h to obtain the CNTs/Fe3O4The/melamine composite carbon foam is black solid powder, and has an XRD (X-ray diffraction) pattern shown in figure 4, an EDS (electron-ray diffraction) spectrum shown in figure 5 and a TEM (transmission electron microscope) pattern shown in figure 6. As can be clearly seen from FIG. 6, the high dispersion of the iron oxide nanoparticles (the dots are iron oxide nanoparticles, and the rest are carbon), and the particle diameter of the sample in FIG. 6 (b) is mainly concentrated in 18.85-34.15 nm. It can be seen from fig. 5 that both Fe and O elements are uniformly distributed.
Comparative example 1
This comparative example differs from example 4 in that step 3 (i.e. in situ growth of Fe-MOF and subsequent carbonization process) is not included, resulting in a CNTs/melamine material.
Comparative example 2
This comparative example is different from example 4 in that step 2 is not included, that is, Fe is obtained by directly using the melamine based carbon foam produced in step 1 as a carbon substrate3O4A melamine material.
Test example
And (3) testing the electromagnetic shielding performance:
the electromagnetic shielding test was performed on the samples obtained in examples 1 to 4 and comparative examples 1 to 2, and the test method was as described above.
The results are shown in table 1, fig. 7 and fig. 8.
TABLE 1
As can be seen from Table 1, CNTs/Fe of example 43O4The electromagnetic shielding performance of the melamine composite foam carbon can reach 46.41 dB.
As can be seen from Table 1 and FIG. 7, the CNTs/melamine material of comparative example 1 has significantly lower electromagnetic shielding performance than the CNTs/Fe material of the examples3O4Melamine, which further illustrates the loading of Fe3O4The electromagnetic shielding performance of the CNTs/melamine material is effectively improved.
To further verify CNTs/Fe3O4Flexibility of melamine composite foam carbon, and CNTs/Fe is detected3O4The compression cycle performance of the melamine composite carbon foam is as follows:
the electromagnetically shielded samples prepared in example 4 and comparative example 2 were slowly pressed using a ruler until the thickness thereof was reduced to 1.5mm, the ruler was removed and it was waited for its original shape, and the above operation was recorded as 1 compression cycle. The carbon foams obtained in example 4 and comparative example 2 were subjected to 0 to 50 compression cycles and examined for the deterioration of their electromagnetic shielding properties.
As shown in FIG. 9, the shielding performance of the composite carbon foam of example 4 was maintained at 33.8dB (72.82% retention of electromagnetic shielding) after 0-50 compression cycles.
As can be seen from FIG. 9, Fe of comparative example 23O4The electromagnetic shielding performance of the melamine material is obviously lower than that of CNTs/Fe3O4Melamine, which further illustrates CNTs/Fe3O4The melamine composite material has excellent electromagnetic shielding performance.
As can be seen from the combination of FIGS. 5 and 6, Fe is prepared by in-situ MOF growth and carbonization3O4The nano particles can be uniformly distributed on the carbon substrate, so that the nano particles are less in shedding in the compression process, and the compression cycle performance of the material is improved.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same. While the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: modifications may be made to the embodiments described above, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the invention as defined by the claims; but such modifications or substitutions are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (10)
1. CNTs/Fe3O4The melamine composite carbon foam is characterized in that the CNTs/Fe3O4The melamine composite carbon foam comprises:
the CNTs/melamine composite carbon base material is composed of a melamine carbon foam framework and carbon nanotubes loaded on the melamine carbon foam framework;
and, Fe3O4The nano particles are dispersed on the CNTs/melamine composite carbon base material;
preferably, the Fe3O4The particle size of the nano-particles is 10-200 nm.
2. The CNTs/Fe of claim 13O4Melamine composite carbon foam, characterized in that the Fe3O4Nano particles in the CNTs/Fe3O4The load capacity of the melamine composite carbon foam is 0.1-20 mg/cm3；
Preferably, the loading capacity of the carbon nano tube on the CNTs/melamine composite carbon base material is 1-8 mg/cm3。
3. CNTs/Fe as defined in claim 1 or 23O4The preparation method of the melamine composite carbon foam is characterized by comprising the following steps:
(1) obtaining melamine carbon foam;
(2) depositing and growing carbon nanotubes on the melamine carbon foam to obtain a CNTs/melamine composite carbon matrix material;
(3) adding iron salt, an organic ligand and an additive into a methanol solvent or a mixed solvent of N, N-dimethylformamide and methanol to obtain a mixed solution, immersing the CNTs/melamine composite carbon base material into the mixed solution, and putting the CNTs/melamine composite carbon base material into a reaction kettle for reaction, so that a nano-grade granular Fe-MOFs material grows in situ on the CNTs/melamine composite carbon base material, and thus CNTs/Fe-MOFs/melamine composite carbon foam is obtained;
(4) carbonizing the CNTs/Fe-MOFs/melamine composite carbon foam to obtain CNTs/Fe3O4Melamine composite carbon foam.
4. The method according to claim 3, wherein the step (1) comprises:
carbonizing melamine sponge to obtain melamine carbon foam;
preferably, the carbonization temperature is 700-900 ℃, and the carbonization time is 1-3 h.
5. The method according to claim 3, wherein the step (2) comprises depositing growing carbon nanotubes on the melamine carbon foam by chemical vapor deposition;
preferably, step (2) comprises:
heating the melamine carbon foam in an inert environment, introducing a ferrocene toluene solution, and depositing and growing a carbon nano tube on the melamine carbon foam through chemical vapor deposition;
preferably, the temperature rise is 700-900 ℃;
preferably, the concentration of ferrocene in the toluene solution of ferrocene is 3-5 wt%;
preferably, the loading capacity of the carbon nano tube on the CNTs/melamine composite carbon base material is 1-8 mg/cm3。
6. The production method according to claim 3, wherein, in the step (3),
the ferric salt is selected from one or more of ferric trichloride hexahydrate, ferric acetate, ferric nitrate and ferric sulfate;
the organic ligand is selected from one or more of terephthalic acid, trimesic acid and 1,2, 4-triazole;
the additive is selected from one or more of trifluoroacetic acid and trifluoromethanesulfonic acid;
preferably, in the step (3),
the volume ratio of the N, N-dimethylformamide to the methanol is 0-1;
preferably, the reaction temperature is 140-160 ℃, and the reaction time is 12-24 h.
7. The production method according to claim 3, wherein, in the step (4),
the carbonization temperature is 500-600 ℃, and the heat preservation time is 2-3 h;
Fe3O4nanoparticles in CNTs/Fe3O4The load capacity of the melamine composite carbon foam is 0.1-20 mg/cm3。
8. CNTs/Fe as defined in claim 1 or 23O4Melamine composite carbon foam or CNTs/Fe prepared by the preparation method of any one of claims 4-73O4The melamine composite carbon foam is applied to electromagnetic shielding.
9. Use according to claim 8, characterised in that CNTs/Fe3O4Total electromagnetic shielding performance SE of melamine composite carbon foamTIs 35-47 dB.
10. Electromagnetic shielding composition, and its preparation methodCharacterized in that it comprises CNTs/Fe as defined in claim 1 or 23O4Melamine composite carbon foam or CNTs/Fe prepared by the preparation method of any one of claims 4-73O4Melamine composite carbon foam.
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