CN114212771B - CNTs/Fe 3 O 4 Melamine composite carbon foam and preparation method and application thereof - Google Patents
CNTs/Fe 3 O 4 Melamine composite carbon foam and preparation method and application thereof Download PDFInfo
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- CN114212771B CN114212771B CN202210014981.XA CN202210014981A CN114212771B CN 114212771 B CN114212771 B CN 114212771B CN 202210014981 A CN202210014981 A CN 202210014981A CN 114212771 B CN114212771 B CN 114212771B
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 162
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 156
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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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 6
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- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
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- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
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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
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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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention provides a CNTs/Fe 3 O 4 Melamine composite carbon foam and a preparation method and application thereof. The invention adopts melamine sponge as raw material, and sequentially carries out carbonization process and in-situ growth carbon nanotube process to prepare flexible carbon matrix material, then carries out in-situ growth of iron-based MOFs crystal material on the surface of the carbon matrix material to obtain CNTs/Fe-MOFs/melamine composite material, and carries out carbonization treatment to obtain flexible CNTs/Fe 3 O 4 Melamine composite carbon foam. The composite carbon foam prepared by the method realizes Fe 3 O 4 The high dispersion of the nanoparticles is advantageous for improving the electromagnetic shielding properties of the syntactic carbon foam. The material is used in the field of electromagnetic shielding and shows excellent electromagnetic shielding performance.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a CNTs/Fe 3 O 4 Melamine 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 transmission and exist in the living space of people. Meanwhile, electromagnetic pollution is inevitably generated in electronic components used in electronic products and various signal towers, and the electromagnetic pollution shortens the service life of electronic equipment and has a certain influence on the sensitivity of the electronic equipment. Since electromagnetic shielding is one of means capable of effectively controlling electromagnetic interference and pollution problems, applying a certain electromagnetic shielding to various electronic products is an optimal solution for preventing electromagnetic pollution from adversely affecting human health and surrounding environment, and thus research on electromagnetic shielding materials is attracting attention.
Because the traditional metal electromagnetic shielding material has the defects of higher density, easy corrosion, high processing difficulty and the like, the matching degree of the traditional metal electromagnetic shielding material for small and miniature equipment is lower, the related research of the electromagnetic shielding material for replacing the metal material is widely focused, wherein the carbon-based material has larger specific surface area, good conductivity, easily-controlled structure, low density, stable chemical property, high temperature resistance and the like, and the related research of the carbon-based electromagnetic shielding material is rapidly developed. The novel electromagnetic shielding material integrating light, thin and high electromagnetic shielding performance is hopeful to be prepared by compounding the carbon material with metal or metal oxide.
Ferrite as a shielding filler, whose main principles of shielding electromagnetic waves are dielectric loss andthe magnetic loss and the high conductivity and the good magnetic permeability in a plurality of frequency ranges of the electromagnetic wave are combined, so that the electromagnetic wave is quickly attenuated after entering the shielding body. As a typical representative of ferrite, fe 3 O 4 Is a ferrite with a typical 'trans' -spinel structure, has outstanding performances in terms of magnetic loss and dielectric loss, and in addition, fe 3 O 4 It also has the advantages of unique surface effect and the like, is widely used as shielding filler. The method comprises the steps of mixing divalent and trivalent ferric salts, and preparing nano Fe by adopting a coprecipitation method 3 O 4 Particles, which are used for preparing nano Fe 3 O 4 Particle-based process, but Fe obtained by the process 3 O 4 The particles have the disadvantage of easy agglomeration, and therefore how to increase Fe 3 O 4 The dispersibility of fine particles becomes a key issue for improving the electromagnetic shielding property thereof.
In view of this, the present invention has been made.
Disclosure of Invention
One of the objects of the present invention is to provide CNTs/Fe 3 O 4 Melamine composite carbon foam, fe 3 O 4 The nanoparticles are highly dispersed on the surface of the carbon matrix.
Another object of the present invention is to provide a CNTs/Fe as described above 3 O 4 Preparation method of melamine composite carbon foam, in-situ growth of nano-grade granular Fe-MOFs material on carbon substrate surface by a specific method, and carbonization of Fe 3 O 4 The nanoparticles are highly dispersed.
Another object of the present invention is to provide an electromagnetic shielding composition comprising the CNTs/Fe 3 O 4 Melamine composite carbon foam or CNTs/Fe prepared by the preparation method 3 O 4 Melamine composite carbon foam.
The fourth object of the present invention is to provide a CNTs/Fe as described above 3 O 4 Melamine composite carbon foam or CNTs/Fe prepared by the preparation method 3 O 4 Use of melamine composite carbon foam for electromagnetic shielding, exhibiting excellent electrical propertiesMagnetic shielding properties.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
one aspect of the present invention provides CNTs/Fe 3 O 4 Melamine composite carbon foam comprising:
the CNTs/melamine composite carbon matrix material consists of a melamine carbon foam skeleton and carbon nanotubes loaded on the melamine carbon foam skeleton;
fe (b) 3 O 4 Nanoparticles dispersed on the CNTs/melamine composite carbon matrix material;
the source of 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 after carbonization of melamine sponge.
The manner of forming the carbon nanotubes 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, carbon nanotubes are deposited and grown on melamine carbon foam using chemical vapor deposition to achieve loading of the carbon nanotubes.
In some embodiments, the carbon nanotubes are loaded on the CNTs/melamine composite carbon matrix material at a loading of 1-8 mg/cm 3 (e.g., 1.6, 2.2, 3.2, 4.0, 4.9, 6.3 mg/cm) 3 )。
Fe of the present invention 3 O 4 Nanoparticles are highly dispersed on the surface of CNTs/melamine composite carbon matrix material, in some embodiments Fe 3 O 4 The particle size of the nanoparticles is 10 to 200nm, preferably 18 to 160nm, more preferably 15 to 50nm, for example 18.85 to 43.73nm.
In some embodiments, highly dispersed Fe 3 O 4 The nano particles are obtained by in-situ growth of nano-grade granular Fe-MOFs material on the surface of CNTs/melamine composite carbon matrix material and carbonization.
Further, in some embodiments, fe 3 O 4 Nanoparticle in CNTs/Fe 3 O 4 The load capacity of the melamine composite carbon foam is 0.1-20 mg/cm 3 。
The loading is expressed as a unit volume (cm) 3 )CNTs/Fe 3 O 4 Fe in melamine composite carbon foam 3 O 4 Weight of nanoparticles (mg), i.e. Fe 3 O 4 Weight of nanoparticles (mg)/(CNTs/Fe) 3 O 4 Volume of melamine composite carbon foam) (cm 3 )。
In another aspect, the present invention provides a process for preparing CNTs/Fe 3 O 4 A method of melamine composite carbon foam comprising the steps of:
(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 ferric 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 matrix material into the mixed solution and putting the mixed solution into a reaction kettle for reaction, so that nano-grade granular Fe-MOFs materials grow on the CNTs/melamine composite carbon matrix material in situ to obtain CNTs/Fe-MOFs/melamine composite carbon foam;
(4) Carbonizing the CNTs/Fe-MOFs/melamine composite carbon foam to obtain CNTs/Fe 3 O 4 Melamine composite carbon foam.
Step (1)
The source of 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 melamine sponge having a corresponding size and shape can be obtained by purchasing or selecting a proper method and condition according to the size required in the application field. In some embodiments, the melamine sponge may be rectangular in shape and may be 90mm long, 28mm wide and 20mm high in size, but is not limited thereto.
The carbonization conditions are not particularly limited, and any conditions in the art that can be carbonized to form a carbon foam may be employed. In some embodiments, the carbonization temperature is 700-900 ℃ (e.g., 700, 800, 900 ℃), and the carbonization time is 1-3 hours (e.g., 1,2, 3 hours).
In one embodiment, step (1) comprises:
cutting commercially available melamine sponge into rectangular solids with the length and the width of 90mm, 28mm and 20mm respectively for later use; soaking the cut sample in ethanol solution, performing ultrasonic oscillation for 30min, repeatedly cleaning for three times, and washing away attached impurities for later use; placing pre-washed melamine sponge into a quartz vessel, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2), the temperature is raised to 700-900 ℃ at a heating rate of 2 ℃/min, and then the carbonization process is carried out in a tubular furnace for 2 hours at constant temperature; after the reaction is completed, waiting for the tubular furnace to naturally cool to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using ethanol solution, and drying the carbon foam to obtain melamine-based carbon foam.
Step (2)
The manner of depositing and growing the carbon nanotubes is not particularly limited, and the carbon nanotubes may be deposited and grown on the melamine carbon foam according to a method known in the art. In some embodiments, carbon nanotubes are grown deposited on melamine carbon foam using chemical vapor deposition;
further, in some embodiments, step (2) comprises:
heating melamine carbon foam in an inert environment, introducing toluene solution of ferrocene, and depositing and growing carbon nano tubes on the melamine carbon foam through chemical vapor deposition;
the temperature of the heating 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 employed. In some embodiments, the ferrocene concentration in the toluene solution of ferrocene is 3-5wt% (e.g., 4 wt%).
In one embodiment, step (2) comprises:
the ferrocene is weighed by an analytical balance in advance, dissolved in toluene to prepare a ferrocene-toluene mixed solution with the weight percent of 4%, and fully and uniformly mixed and placed at normal temperature for standby.
Placing the prepared melamine-based carbon foam above an iron wire tray, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2), the temperature is raised to 800 ℃ at a heating rate of 4 ℃/min. At this time, the flow rate 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 2 The mixed vapor carrying ferrocene and toluene flows through the whole tube furnace, and Carbon Nanotubes (CNTs) are grown by Chemical Vapor Deposition (CVD) at constant temperature for 3h.
In the obtained CNTs/melamine composite carbon matrix material, the loading capacity of the carbon nano tube on the CNTs/melamine composite carbon matrix material is 1-8 mg/cm 3 。
Step (3)
In this step, nano-sized granular Fe-MOFs material (crystalline Fe-MOFs material) is grown in situ on the CNTs/melamine composite carbon matrix material, and subsequent carbonization can form highly dispersed Fe 3 O 4 And (3) nanoparticles.
The iron salt may be a precursor known in the art for synthesizing Fe metal portions of Fe-MOFs materials, including but not limited to ferric trichloride hexahydrate, ferric acetate, ferric nitrate, ferric sulfate, and the like.
The organic ligands may be those known in the art to be useful as MOFs materials bridged with Fe metal moieties, including but not limited to terephthalic acid, trimesic acid, 1,2, 4-triazole, and the like.
The additives may be materials added during the synthesis of MOFs materials known in the art, including but not limited to trifluoroacetic acid, trifluoromethanesulfonic acid, and the like.
In the process of synthesizing MOFs material, methanol or a mixture of N, N-dimethylformamide and methanol is selected as a solvent to regulate the structural morphology of MOFs material, so that the MOFs material forms crystal MOFs, and the MOF crystal is promoted to generate structural defects, and the solvent not only serves as a guest molecule in the MOF synthesis process, but also has a remarkable influence on the structure of the MOF material. For example, two MOF-5 cuboid solutions synthesized in different solvent systems, N, N-Dimethylformamide (DMF) solutions, can form dense MOF crystals, and N, N-Diethylformamide (DEF) solutions can form MOF cuboids similar to mesogens, indicating that solvents have a large impact on the surface morphology and internal structure of MOF-5 cuboids and can create structural defects in MOF crystals.
In some embodiments, the volume ratio of N, N-dimethylformamide to methanol is 0-1, for example, the volume ratio of the two may be 1:4, 2:3, 1:1, but is not limited thereto. When the volume ratio is 0, it means that only methanol is used as a solvent.
In some embodiments, the reaction temperature is 150 ℃ and the reaction time is 24 hours.
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 for three hours at normal temperature, immersing CNTs/melamine composite carbon foam into the mixed solution, putting the mixed solution into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene together, reacting for 24 hours at 150 ℃, naturally cooling, cleaning a reaction product with N, N-dimethylformamide and absolute ethyl alcohol, carrying out 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 known method in the art can be used which can carbonize Fe-MOFs to form C and Fe 3 O 4 Is a condition of (2). In some embodiments, the carbonization temperature is 500-600 ℃ (e.g., 500, 550, 600 ℃), and the carbonization time is 1-3 hours (e.g., 1,2, 3 hours)。
In one embodiment, step (4) comprises:
putting CNTs/Fe-MOFs/melamine composite carbon foam material into a quartz tube in a porcelain boat, then heating to 550 ℃ under the condition of argon atmosphere in a tube furnace at the heating condition of 5 ℃/min, and preserving heat for 2 hours to obtain CNTs/Fe 3 O 4 The melamine composite carbon foam material is black solid powder.
By comparison of CNTs/Fe 3 O 4 The weight difference between the melamine composite carbon foam and the CNTs/melamine can obtain Fe 3 O 4 Divided by CNTs/Fe 3 O 4 The volume of the melamine composite carbon foam is used for obtaining the corresponding Fe 3 O 4 The load amount.
The obtained CNTs/Fe 3 O 4 In the melamine composite carbon foam, fe 3 O 4 Nanoparticle in CNTs/Fe 3 O 4 The load capacity of the melamine composite carbon foam is 0.1-20 mg/cm 3 。
The loading is expressed as a unit volume (cm) 3 )CNTs/Fe 3 O 4 Fe in melamine composite carbon foam 3 O 4 Weight of nanoparticles (mg), i.e. Fe 3 O 4 Weight of nanoparticles (mg)/(CNTs/Fe) 3 O 4 Volume (cm) of melamine-based composite carbon foam 3 )。
In still another aspect, the present invention provides an electromagnetic shielding composition comprising the CNTs/Fe as described above 3 O 4 Melamine composite carbon foam or CNTs/Fe prepared by the preparation method 3 O 4 Melamine composite carbon foam.
The electromagnetic shielding composition can be prepared into a composite electromagnetic shielding material by adding graphene, a composite electromagnetic shielding material by adding carbon nanotubes, or a composite electromagnetic shielding material by adding ferrite, for example. The electromagnetic shielding composition may also contain additives, such as Fe, depending on the particular application 3 O 4 Graphene, nanotubes, alpha-Fe 2 O 3 。
The inventionIn yet another aspect, there is provided a CNTs/Fe as described above 3 O 4 Melamine composite carbon foam or CNTs/Fe prepared by the preparation method 3 O 4 Use of melamine composite carbon foam in electromagnetic shielding.
The electromagnetic shielding performance test method comprises the following steps:
the test specimens were cut into 10.1X12.8X3.0 mm blocks and the melamine-based carbon foam specimens were subjected to solid material reflectance, i.e.S parameters (S 11 ，S 21 ) And detecting, and setting the transmitting power to be-5 dB. Electromagnetic shielding parameters are calculated. The specific calculation formula is as follows:
SE T ＝SE R +SE A (1)
SE R ＝-10log 10 (1-R) (2)
SE A ＝-10log 10 [T/(1-R)] (3)
R＝10(S 11 /10) (4)
T＝10(S 21 /10) (5)
A＝1-R-T
wherein: SE (SE) T Total electromagnetic shielding performance, dB;
SE R -material surface reflection loss, dB;
SE A -absorption loss inside the material, dB;
r—material reflectance (%);
a-material absorption (%);
t-material transmittance (%);
CNTs/Fe of the present invention 3 O 4 Total electromagnetic shielding performance SE of melamine composite carbon foam T Can reach 35-47 dB, and is a light, thin and soft 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 MelamineCarbon-based foam, carbon Nanotubes (CNTs) are loaded on a carbon structure skeleton of the carbon-based foam, then the CNTs/Fe-MOFs/melamine composite material is obtained through in-situ growth of a metal Fe organic skeleton material (Fe-MOFs) on a CNTs/melamine composite carbon matrix material, and finally Fe is obtained through further carbonization treatment 3 O 4 CNTs/Fe with nano particles highly dispersed on surface of carbon matrix 3 O 4 Melamine composite material. Electromagnetic shielding performance tests show that the material disclosed by the invention is a light, thin and soft type high-performance electromagnetic shielding material.
(2) The invention forms crystalline Fe-MOFs by regulating and controlling MOFs materials in the synthesis process, and generates C and Fe just after further carbonization 3 O 4 Fe is realized 3 O 4 The nanoparticles are highly dispersed.
The present invention has been described in detail hereinabove, but the above embodiments are merely exemplary 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 summary or the following examples.
Unless explicitly stated otherwise, numerical ranges throughout this application include any subrange therein and any numerical value incremented by the smallest subunit in which a given value is present. Unless explicitly stated otherwise, numerical values throughout this application represent approximate measures or limits to include minor deviations from the given value and ranges of embodiments having about the stated value and having the exact value noted. Except in the operating examples provided last, all numerical values of parameters (e.g., amounts or conditions) in this application (including the appended claims) are to be understood in all cases as modified by the term "about" whether or not "about" actually appears before the numerical value. "about" means that the recited value allows for slight imprecision (with some approximation to the exact value; approximately or reasonably close to the value; approximated). "about" as used herein at least means variations that can be produced by ordinary methods of measuring and using these parameters if the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" may include a change 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 a CNTs/melamine composite carbon foam according to example 2 of the present invention, wherein a is a CNTs/melamine composite carbon foam low-magnification SEM image, b is a CNTs/melamine composite carbon foam high-magnification SEM image, c is a CNTs/melamine composite carbon foam surface-loaded carbon nanotube SEM image;
FIG. 2 is a Scanning Electron Microscope (SEM) of the invention for preparing Fe-MOFs material at different DMF and methanol ratios, wherein a is a scanning electron microscope of the invention for preparing Fe-MOFs material at DMF and methanol ratio of example 3, b is a scanning electron microscope of the invention for preparing Fe-MOFs material at DMF and methanol ratio of example 2, c is a scanning electron microscope of the invention for preparing Fe-MOFs material at DMF and methanol ratio of example 1, d is a scanning electron microscope of the invention for preparing Fe-MOFs material at DMF and methanol ratio of example 4;
FIG. 3 is an XRD pattern of CNTs/Fe-MOFs/melamine composite carbon foam materials prepared with different DMF and methanol ratios according to the present invention;
FIG. 4 shows CNTs/Fe prepared in example 4 of the present invention 3 O 4 XRD pattern of melamine composite carbon foam;
FIG. 5 shows CNTs/Fe prepared in example 4 of the present invention 3 O 4 EDS spectrum of melamine composite carbon foam, wherein a is CNTs/Fe 3 O 4 SEM picture of melamine composite carbon foam, b is corresponding Fe element distribution diagram, c is corresponding O element distribution diagram;
FIG. 6 shows the synthesis of CNTs/Fe from (methanol) according to example 4 of the present invention 3 O 4 TEM image of 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 examples 3 O 4 Total electromagnetic shielding performance (SE) of melamine composite carbon foam in the X-band T )；
FIG. 8 is a view of nothingWith Fe 3 O 4 CNTs/Fe loaded 3 O 4 Electromagnetic shielding average value SE of melamine composite carbon foam in X wave band T 、SE A 、SE R ；
FIG. 9 shows CNTs/Fe prepared in example 4 of the present invention 3 O 4 Melamine composite carbon foam and Fe prepared in comparative example 2 3 O 4 Residual barrier properties after 0-50 compression cycles of the melamine material.
Detailed Description
The 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 as claimed.
Except special description, the raw materials, reagents, methods and the like adopted in the examples are all conventional in the field, the experiment is carried out except for melamine sea, other medicines are all from microphone reagents, and melamine sponge is purchased from Shanghai Beiyou building materials Co., ltd;
TEM was obtained using JEM-2100 from JEOL corporation, japan, scanning Electron Microscope (SEM) and energy spectrum analysis (EDS) data using a field emission SU-70 microscope, and XRD test was obtained using a Bruker D8 advanced diffractometer.
Example 1
CNTs/Fe 3 O 4 The preparation method of the melamine composite carbon foam comprises the following steps:
1. cutting melamine sponge into rectangular solid with length, width and thickness of 90mm, 28mm and 20mm respectively for standby. Soaking the cut sample in ethanol solution, performing ultrasonic oscillation for 30min, repeatedly cleaning for three times, and washing off attached impurities for later use. Placing pre-washed melamine sponge into a quartz vessel, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2) C/min, the temperature is raised to 700 ℃ at a heating rate of 2 ℃ per minute, and then the carbonization process is carried out in a tubular furnace at constant temperature for 2 h. After the reaction is completed, waiting for the tubular furnace to naturally cool to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using ethanol solution, and drying the carbon foam to obtain melamine-based carbon foam.
2. The ferrocene is weighed by an analytical balance in advance, dissolved in toluene to prepare a ferrocene-toluene mixed solution with the weight percent of 4%, and fully and uniformly mixed and placed at normal temperature for standby.
Placing the prepared melamine-based carbon foam above an iron wire tray, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2), the temperature is raised to 800 ℃ at a heating rate of 4 ℃/min. At this time, the flow rate 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 2 The mixed vapor carrying ferrocene and toluene flows through the whole tube furnace, and Carbon Nanotubes (CNTs) are grown by Chemical Vapor Deposition (CVD) at constant temperature for 3h.
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: methanol=1/4), the mixture is stirred for three hours at normal temperature, CNTs/melamine composite carbon foam is immersed into the mixed solution, the mixture is put into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene together, the reaction kettle is naturally cooled after being reacted for 24 hours at 150 ℃, the reaction product is washed by the N, N-dimethylformamide and absolute ethyl alcohol, and then the reaction product is subjected to suction filtration and drying, so that the CNTs/Fe-MOFs/melamine composite carbon foam material is obtained, and an XRD diagram is shown in a graph of FIG. 3.
As can be seen by comparing XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOF, the addition of the CNTs/melamine composite carbon foam material does not affect the growth of the Fe-MOF material.
The Fe-MOFs material is obtained by directly adopting the step 3 without the steps 1 and 2, 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 into a porcelain boat, placing the porcelain boat into a quartz tube, and then heating to 550 ℃ under the condition of argon atmosphere in a tube furnace at the heating condition of 5 ℃/min for 2h, thereby obtaining CNTs/Fe 3 O 4 Melamine composite carbon foam is black solid powder.
Example 2
CNTs/Fe 3 O 4 The preparation method of the melamine composite carbon foam comprises the following steps:
1. cutting melamine sponge into rectangular solid with length, width and thickness of 90mm, 28mm and 20mm respectively for standby. Soaking the cut sample in ethanol solution, performing ultrasonic oscillation for 30min, repeatedly cleaning for three times, and washing off attached impurities for later use. Placing pre-washed melamine sponge into a quartz vessel, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2) C/min, the temperature is increased to 800 ℃ at a heating rate of 2 ℃ per minute, and then the carbonization process is carried out in a tubular furnace at constant temperature for 2 h. After the reaction is completed, waiting for the tubular furnace to naturally cool to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using ethanol solution, and drying the carbon foam to obtain melamine-based carbon foam.
2. The ferrocene is weighed by an analytical balance in advance, dissolved in toluene to prepare a ferrocene-toluene mixed solution with the weight percent of 4%, and fully and uniformly mixed and placed at normal temperature for standby.
Placing the prepared melamine-based carbon foam above an iron wire tray, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2), the temperature is raised to 800 ℃ at a heating rate of 4 ℃/min. At this time, the flow rate 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 2 The mixed vapor carrying ferrocene and toluene flows through the whole tube furnace, and Carbon Nanotubes (CNTs) are grown by Chemical Vapor Deposition (CVD) at constant temperature for 3 hours, and the obtained CNTs/melamine composite carbon foam SEM is shown in figure 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: methanol=2/3), the mixture is stirred for three hours at normal temperature, CNTs/melamine composite carbon foam is immersed into the mixed solution, the mixture is put into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene together, the reaction kettle is naturally cooled after being reacted for 24 hours at 150 ℃, the reaction product is washed by the N, N-dimethylformamide and absolute ethyl alcohol, and then the reaction product is subjected to suction filtration and drying, so that the CNTs/Fe-MOFs/melamine composite carbon foam material is obtained, and an XRD diagram is shown in a graph of FIG. 3.
The Fe-MOFs material is obtained by directly adopting the step 3 without the steps 1 and 2, and the XRD pattern of the Fe-MOFs material is shown as b in figure 2.
As can be seen by comparing XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOF, the addition of the CNTs/melamine composite carbon foam material does not affect the growth of the Fe-MOF material.
4. Weighing a certain amount of CNTs/Fe-MOFs/melamine composite carbon foam material into a porcelain boat, placing the porcelain boat into a quartz tube, and then heating to 550 ℃ at a heating condition of 5 ℃/min under an argon atmosphere condition in a tube furnace, and preserving heat for 2 hours to obtain CNTs/Fe 3 O 4 Melamine composite carbon foam is black solid powder.
Example 3
CNTs/Fe 3 O 4 The preparation method of the melamine composite carbon foam comprises the following steps:
1. cutting melamine sponge into rectangular solid with length, width and thickness of 90mm, 28mm and 20mm respectively for standby. Soaking the cut sample in ethanol solution, performing ultrasonic oscillation for 30min, repeatedly cleaning for three times, and washing off attached impurities for later use. Placing pre-washed melamine sponge into a quartz vessel, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2) C/min, the temperature is increased to 850 ℃ at a heating rate of 2 ℃ per minute, and then the carbonization process is carried out in a tubular furnace at constant temperature for 2 h. After the reaction is completed, waiting for the tubular furnace to naturally cool to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using ethanol solution, and drying the carbon foam to obtain melamine-based carbon foam.
2. The ferrocene is weighed by an analytical balance in advance, dissolved in toluene to prepare a ferrocene-toluene mixed solution with the weight percent of 4%, and fully and uniformly mixed and placed at normal temperature for standby.
Placing the prepared melamine-based carbon foam above an iron wire tray, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2), the temperature is raised to 800 ℃ at a heating rate of 4 ℃/min. At this time, the flow rate 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 2 The mixed vapor carrying ferrocene and toluene flows through the whole tube furnace, and Carbon Nanotubes (CNTs) are grown by Chemical Vapor Deposition (CVD) at constant temperature for 3h.
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 mixed solution and the CNTs/melamine composite carbon foam and the mixed solution are put into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene together, the reaction kettle is naturally cooled after being reacted for 24 hours at 150 ℃, the reaction product is washed by the N, N-dimethylformamide and absolute ethyl alcohol, and the reaction product is subjected to suction filtration and drying, so that the CNTs/Fe-MOFs/melamine composite carbon foam material is obtained, and an XRD diagram is shown in a graph of FIG. 3.
As can be seen by comparing XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOFs, the addition of the CNTs/melamine composite carbon foam material did not affect the growth of the Fe-MOF material.
The Fe-MOFs material is obtained by directly adopting the step 3 without the steps 1 and 2, 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 into a porcelain boat, placing the porcelain boat into a quartz tube, and then heating to 550 ℃ under the condition of argon atmosphere in a tube furnace at the heating condition of 5 ℃/min for 2h, thereby obtaining CNTs/Fe 3 O 4 Melamine composite carbon foam is black solid powder.
Example 4
CNTs/Fe 3 O 4 The preparation method of the melamine composite carbon foam comprises the following steps:
1. cutting melamine sponge into rectangular solid with length, width and thickness of 90mm, 28mm and 20mm respectively for standby. Soaking the cut sample in ethanol solution, performing ultrasonic oscillation for 30min, repeatedly cleaning for three times, and washing off attached impurities for later use. Placing pre-washed melamine sponge into a quartz vessel, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2) C/min, the temperature is increased to 900 ℃ at a heating rate of 2 ℃ per minute, and then the furnace is provided with a tube furnaceAnd (5) carrying out carbonization process at internal constant temperature for 2 h. After the reaction is completed, waiting for the tubular furnace to naturally cool to room temperature, taking out the carbon foam, ultrasonically washing the carbon foam for 30min by using ethanol solution, and drying the carbon foam to obtain melamine-based carbon foam.
2. The ferrocene is weighed by an analytical balance in advance, dissolved in toluene to prepare a ferrocene-toluene mixed solution with the weight percent of 4%, and fully and uniformly mixed and placed at normal temperature for standby.
Placing the prepared melamine-based carbon foam above an iron wire tray, transferring into a tube furnace, and adding high-purity N 2 Under the protection of (2), the temperature is raised to 800 ℃ at a heating rate of 4 ℃/min. At this time, the flow rate 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 2 The mixed vapor carrying ferrocene and toluene flows through the whole tube furnace, and Carbon Nanotubes (CNTs) are grown by Chemical Vapor Deposition (CVD) at constant temperature for 3h.
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), stirred at normal temperature for three hours, CNTs/melamine composite carbon foam is immersed into the mixed solution, and put into a sealed stainless steel reaction kettle lined with polytetrafluoroethylene together, reacted for 24 hours at 150 ℃ and then naturally cooled, the reaction product is washed by N, N-dimethylformamide and absolute ethyl alcohol, suction filtration and drying are carried out, and the CNTs/Fe-MOFs/melamine composite carbon foam material is obtained, and the XRD pattern is shown in figure 3.
As can be seen by comparing the XRD patterns of the CNTs/Fe-MOFs/melamine composite carbon foam material and the Fe-MOFs material, the addition of CNTs/melamine composite carbon foam material did not affect the growth of the Fe-MOF material.
The Fe-MOFs material is obtained by directly adopting the step 3 without the steps 1 and 2, 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 into a porcelain boat, placing the porcelain boat into a quartz tube, and then heating to 550 ℃ under the condition of argon atmosphere in a tube furnace at the heating condition of 5 ℃/min for 2h, thereby obtaining CNTs/Fe 3 O 4 The melamine composite carbon foam is black solid powder, the XRD diagram is shown in figure 4, the EDS energy spectrum is shown in figure 5, and the TEM diagram is shown in figure 6. As can be clearly seen in fig. 6, the highly dispersed iron oxide nanoparticles (spots are iron oxide nanoparticles, and elsewhere are carbon), and the sample particle diameter in fig. 6 (b) is mainly concentrated at 18.85 to 34.15nm. Fig. 5 shows 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 the Fe-MOF and subsequent carbonization process) is not included, resulting in a CNTs/melamine material.
Comparative example 2
The comparative example differs from example 4 in that step 2 is not included, i.e., melamine-based carbon foam produced in step 1 is directly used as a carbon matrix to obtain Fe 3 O 4 Melamine material.
Test case
Electromagnetic shielding performance test:
the samples obtained in examples 1-4 and comparative examples 1-2 were subjected to electromagnetic shielding testing 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 4 3 O 4 The electromagnetic shielding performance of the melamine composite foam carbon can reach 46.41dB.
As can be seen from Table 1 and FIG. 7, the electromagnetic shielding properties of the CNTs/melamine material of comparative example 1 are significantly lower than those of the CNTs/Fe material of the examples 3 O 4 Melamine, which further illustrates Fe loading 3 O 4 Effectively improves the electromagnetic shielding performance of CNTs/melamine materials.
To further verify CNTs/Fe 3 O 4 Melamine composite foam carbonIs tested for CNTs/Fe 3 O 4 The compression cycle performance of the melamine composite carbon foam is as follows:
the electromagnetic shielding samples prepared in example 4 and comparative example 2 were slowly pressed using a ruler until their thickness was reduced to 1.5mm, and the ruler was removed and waited for its recovery, which was recorded as 1 compression cycle. The carbon foam obtained in example 4 and comparative example 2 was subjected to 0 to 50 compression cycles and examined for attenuation of electromagnetic shielding properties.
As a result, as shown in fig. 9, the shielding performance of the composite carbon foam of example 4 was maintained at 33.8dB (electromagnetic shielding retention rate 72.82%) after 0 to 50 compression cycles.
As can be seen from FIG. 9, fe of comparative example 2 3 O 4 The electromagnetic shielding performance of the melamine material is obviously lower than that of CNTs/Fe 3 O 4 Melamine, which further illustrates CNTs/Fe 3 O 4 Melamine composite materials have excellent electromagnetic shielding properties.
It can also be seen from FIGS. 5 and 6 that Fe is produced by in situ growth of MOF and carbonization 3 O 4 The nano particles can be uniformly distributed on the carbon matrix, so that the nano particles are less in falling off in the compression process, and the compression cycle performance of the material is improved.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limited thereto. Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention as defined in the claims; and such modifications or substitutions are intended to be within the scope of the present invention as defined by the claims.
Claims (9)
1. CNTs/Fe 3 O 4 Melamine composite carbon foam characterized in that the CNTs/Fe 3 O 4 The melamine composite carbon foam comprises:
the CNTs/melamine composite carbon matrix material consists of a melamine carbon foam skeleton and carbon nanotubes loaded on the melamine carbon foam skeleton;
fe (b) 3 O 4 Nanoparticles dispersed on the CNTs/melamine composite carbon matrix material;
the Fe is 3 O 4 The particle size of the nano particles is 15-50 nm;
the CNTs/Fe 3 O 4 The melamine composite carbon foam is prepared by a method comprising the following steps:
(1) Obtaining melamine carbon foam;
(2) Heating the melamine carbon foam in an inert environment to 700-900 ℃, introducing toluene solution of ferrocene, and depositing and growing carbon nano tubes on the melamine carbon foam by chemical vapor deposition to obtain a CNTs/melamine composite carbon matrix material; the loading capacity of the carbon nano tube on the CNTs/melamine composite carbon matrix material is 1-8 mg/cm 3 ；
(3) Adding ferric 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 matrix material into the mixed solution and putting the mixed solution into a reaction kettle for reaction, so that nano-grade granular Fe-MOFs materials grow on the CNTs/melamine composite carbon matrix material in situ to obtain CNTs/Fe-MOFs/melamine composite carbon foam; 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 one or more of trifluoroacetic acid and trifluoromethanesulfonic acid; the reaction temperature is 140-160 ℃, and the reaction time is 12-24 hours;
(4) Carbonizing the CNTs/Fe-MOFs/melamine composite carbon foam to obtain CNTs/Fe 3 O 4 Melamine composite carbon foam; the carbonization temperature is 500-600 ℃, and the heat preservation time is 2-3 hours; fe (Fe) 3 O 4 Nanoparticle in CNTs/Fe 3 O 4 On melamine composite carbon foamThe load is 0.1-20 mg/cm 3 。
2. The CNTs/Fe according to claim 1 3 O 4 The preparation method of the melamine composite carbon foam is characterized by comprising the following steps:
(1) Obtaining melamine carbon foam;
(2) Heating the melamine carbon foam in an inert environment to 700-900 ℃, introducing toluene solution of ferrocene, and depositing and growing carbon nano tubes on the melamine carbon foam by chemical vapor deposition to obtain a CNTs/melamine composite carbon matrix material; the loading capacity of the carbon nano tube on the CNTs/melamine composite carbon matrix material is 1-8 mg/cm 3 ；
(3) Adding ferric 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 matrix material into the mixed solution and putting the mixed solution into a reaction kettle for reaction, so that nano-grade granular Fe-MOFs materials grow on the CNTs/melamine composite carbon matrix material in situ to obtain CNTs/Fe-MOFs/melamine composite carbon foam; 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 one or more of trifluoroacetic acid and trifluoromethanesulfonic acid; the reaction temperature is 140-160 ℃, and the reaction time is 12-24 hours;
(4) Carbonizing the CNTs/Fe-MOFs/melamine composite carbon foam to obtain CNTs/Fe 3 O 4 Melamine composite carbon foam; the carbonization temperature is 500-600 ℃, and the heat preservation time is 2-3 hours; fe (Fe) 3 O 4 Nanoparticle in CNTs/Fe 3 O 4 The load capacity of the melamine composite carbon foam is 0.1-20 mg/cm 3 。
3. The method of claim 2, wherein step (1) comprises:
carbonizing the melamine sponge to obtain melamine carbon foam.
4. The method according to claim 3, wherein the carbonization temperature is 700 to 900 ℃ and the carbonization time is 1 to 3 hours.
5. The preparation method according to claim 2, wherein the concentration of ferrocene in the toluene solution of ferrocene is 3-5wt%.
6. The process according to claim 2, wherein in step (3),
the volume ratio of the N, N-dimethylformamide to the methanol is 0-1.
7. The CNTs/Fe according to claim 1 3 O 4 Melamine composite carbon foam or CNTs/Fe prepared by the preparation method of any one of claims 2-6 3 O 4 Use of melamine composite carbon foam in electromagnetic shielding.
8. The use according to claim 7, wherein CNTs/Fe 3 O 4 Total electromagnetic shielding performance of melamine composite carbon foamSE T 35-47 dB.
9. An electromagnetic shielding composition comprising CNTs/Fe according to claim 1 3 O 4 Melamine composite carbon foam or CNTs/Fe prepared by the preparation method of any one of claims 2-6 3 O 4 Melamine composite carbon foam.
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