CN114349060B - Preparation method of carbon-coated magnetic nanoparticle nitrogen-doped magnetic graphene - Google Patents
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 238000000227 grinding Methods 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
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- 239000003575 carbonaceous material Substances 0.000 abstract description 14
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- 239000002184 metal Substances 0.000 abstract description 2
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- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 18
- 239000002105 nanoparticle Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
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- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the field of preparation of magnetic carbon materials, and particularly relates to a preparation method of nitrogen-doped magnetic graphene carrying carbon-coated magnetic nanoparticles. In order to solve the problem of poor stability of the magnetic graphene, molecules capable of simultaneously providing a carbon source and a nitrogen source are used as raw materials, metallocene such as ferrocene is used as a catalyst, the metallocene is sublimated and decomposed in the heating process, and nitrogen-containing and carbon-containing molecules around the transition metal atoms catalyze to form a nitrogen-doped graphene sheet layer, and meanwhile, a simple substance of the transition metal coated with carbon, a metal oxide or a metal carbide is formed.
Description
Technical Field
The invention belongs to the field of preparation of magnetic carbon materials, and particularly relates to a preparation method of nitrogen-doped magnetic graphene carrying carbon-coated magnetic nanoparticles.
Background
Due to the development of modern technology, military is faced with the military requirement of electromagnetic protection and wave absorption stealth, life is faced with electromagnetic radiation pollution, and development of efficient electromagnetic shielding materials and wave absorption materials is urgent, so that the magnetic material requirement is also very vigorous.
Graphene is a two-dimensional carbon material, and has a series of excellent properties such as light transmission, electric conduction, heat conduction, high strength, high toughness, high specific surface area and the like, and is attracting attention. Magnetic graphene is a novel magnetic carbon material combining the advantages of magnetism and graphene, and is attracting attention in the fields of catalysts (carriers), heavy metal ion adsorption, biological medicine, RNA protection, wave absorption, electromagnetic protection, heat conduction, phase change energy storage and the like. Magnetic graphene belongs to a magnetic carbon material.
The preparation method of the magnetic carbon material can be summarized into the following 5 types: coprecipitation, hydrothermal, template, impregnation and carbonization of metal organic framework materials. The coprecipitation method is to dip a pre-synthesized carbon material into a magnetic precursor solution, and then deposit a magnetic nano material in situ in pore channels of a porous carbon material, thereby synthesizing the magnetic carbon material. The hydrothermal method is to mix the magnetic source and the carbon source in a certain proportion and put them into a high-pressure reaction kettle, and then to make hydrothermal reaction under the condition of high temperature and high pressure so as to obtain the target product. The template method is a kind of synthesis method for constructing the structure and the morphology of a material by taking a substance with a specific structure and morphology as a template and taking template molecules as a main body, and can be divided into a soft template, a hard template and a dual-template method according to different templates. When the magnetic carbon material is prepared by a template method, a magnetic precursor can be introduced during or after synthesis of the carbon material. The impregnation method is simple, the carbon material precursor or the biomass powder is directly impregnated into the magnetic source precursor or the magnetic nanoparticle dispersion solution, the volatile solvent is dried and then is directly subjected to heat treatment, and the magnetic carbon material can be obtained through activation treatment. The metal organic framework material is a novel porous material formed by self-assembling metal ions and organic ligands through coordination bonds, and has developed pore channels and higher specific surface area. Since both the carbon source and the magnetic source exist, the direct carbonization of the metal-organic framework material becomes a novel synthetic method of the magnetic carbon material which appears in recent years.
The synthesis method of the magnetic graphene is similar and can be generally classified into a one-step method and a two-step method. The graphene oxide and the magnetic source precursor are subjected to hydrothermal treatment together to obtain the graphene oxide magnetic source magnetic material. The two-step method is to synthesize ferroferric oxide nano particles firstly, then to compound with graphene oxide or graphene, and then to heat treat, or to synthesize graphene firstly, to mix with a magnetic source precursor, and to obtain magnetic graphene through coprecipitation in solution. There are also patent proposals to replace potassium permanganate with potassium ferrate to prepare graphene oxide containing iron oxide, and then directly obtain the technological path of magnetic graphene through heat treatment. Existing magnetic stoneNanometer Fe in graphene product 3 O 4 The particles are mostly exposed, have high chemical activity, are easily oxidized in the air and are easily dissolved in weak acid solution, so that the magnetic graphene composite material loses magnetism, and the stable magnetic graphene material is difficult to obtain.
Disclosure of Invention
The invention aims to provide a preparation method of carbon-coated magnetic nanoparticle nitrogen-doped magnetic graphene.
The main technical principle of the invention is as follows: molecules capable of simultaneously providing a carbon source and a nitrogen source are used as raw materials, metallocene such as ferrocene is used as a catalyst, the metallocene is sublimated and decomposed in the heating process, and nitrogen-doped graphene sheets are formed by catalyzing surrounding nitrogen-containing and carbon-containing molecules through transition metal atoms, and meanwhile, carbon-coated transition metal simple substances or metal oxides or metal carbides are formed.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
(1) Taking molecules capable of simultaneously providing a carbon source and a nitrogen source as raw materials, taking metallocene as a catalyst, and uniformly mixing to obtain a mixture of the raw materials and the catalyst;
(2) The mixture of the raw materials and the catalyst is uniformly dispersed in a sealable reaction vessel in the atmosphere with the oxygen content of 0-30% (volume fraction), and is placed in the reaction vessel for heat treatment after being sealed, and after naturally cooled to room temperature, the product is taken out, namely the carbon-coated magnetic nanoparticle nitrogen-doped magnetic graphene is obtained.
Further, in the step (1), molecules capable of simultaneously providing a carbon source and a nitrogen source are one or a mixture of more than one of melamine, urea, thiourea, dicyandiamide and cyanuric acid according to any ratio, and the metallocene is one or a mixture of more than one of ferrocene, nickel-dicyclopentadienyl or cobalt-dicyclopentadienyl according to any ratio; the mass ratio of the raw materials to the catalyst is 100:1-100.
Further, the mixture of the raw material, the catalyst and the sealable in the step (2)The mass volume ratio of the effective volume in the reaction vessel is 1-100 g/L, and the stacking thickness of the mixture of the raw materials and the catalyst in the sealable reaction vessel is 0.01-1 g/cm 2 。
Further, the sealable reaction vessel in the step (2) is cylindrical in shape, the sealable reaction vessel is made of a high temperature resistant material, and the sealable reaction vessel in the step (2) is sealed by one or a combination of threads, a grinding port, a graphite sealing strip or a flange.
Still further, the high temperature resistant material is graphite, stainless steel, ceramic, quartz glass.
Furthermore, the reaction device in the step (2) is an electric furnace and an electromagnetic furnace, and the heating cavity of the electric furnace can be any of cuboid, tubular, circular and the like which can put down the reaction container.
When the reaction device is an electric furnace, the heat treatment is specifically as follows: raising the temperature to 650-1000 ℃ for 1-10 h, keeping the constant temperature for 10 min-10 h, and lowering the temperature to 500 ℃ by adopting 1-10 ℃/min; when the reaction device is an induction cooker, the specific heat treatment is as follows: heating to 650-1000 deg.c for 30 s-5 min.
Furthermore, the reaction device is an electric furnace, the sealable reaction container is made of graphite and is carried out under inert protective atmosphere, such as argon, nitrogen or helium, and other reaction containers have no limitation on whether protective atmosphere exists or not, namely, the heat treatment can be carried out in air.
The number of layers of graphene in the magnetic graphene is 1-10.
The magnetic nano particles are metal oxides, simple substances or carbide nano particles of iron, cobalt and nickel, the carbon coating is a carbon layer coating the surface of the magnetic nano particles, and the thickness of the carbon layer is 6-7 layers.
Compared with the prior art, the invention has the following advantages:
the magnetic graphene prepared by the method has the advantages of low product cost, simple process, easy operation, good repeatability and large-scale production, is high in graphene quality (the graphene layer is 6-7 layers of graphene), has good structural stability and chemical stability because the magnetic nano particles are wrapped by the nano carbon layers (6-7 layers), is resistant to acid-base corrosion and air oxidation, and can have long-term magnetic performance. The long-term stability of the common magnetic material is poor, namely, the magnetic nano particles are corroded and the magnetism is weakened after being exposed to the air.
Drawings
FIG. 1 is a scanning electron micrograph of the product of example 1;
FIG. 2 is an X-ray diffraction pattern of the product of example 1;
FIG. 3 is a transmission electron micrograph of the product of example 1;
FIG. 4 is a high resolution transmission electron micrograph of the product of example 1;
FIG. 5 shows the magnetic properties of the product of example 1.
Detailed Description
Example 1
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 1.5g melamine as raw material, taking 0.5g ferrocene as catalyst, mixing uniformly, placing into a grinding-port sealable quartz tank with an effective internal volume of 100mL in an air atmosphere (oxygen content of 22%), and stacking to a thickness of 0.2g/cm 2 Sealing, placing in a muffle furnace, heating to 800 ℃ for 3h, keeping the temperature constant for 2h, cooling to 500 ℃ at 10 ℃/min, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Fig. 1 is a scanning electron micrograph of the product of example 1, and it can be seen from fig. 1 that innumerable nanoparticles are supported on graphene sheets prepared from melamine as a raw material, and the particle size distribution is about 10 to 30nm.
FIG. 2 is an X-ray diffraction pattern of the product of example 1, a comparative standardThe quasi-substance card can see C corresponding to characteristic peaks in XRD patterns 0.08 Fe 1.92 Indicating that the magnetic nanoparticles in the sample are C 0.08 Fe 1.92 (pdf card number 44-1291);
FIG. 3 is a transmission electron micrograph of the product of example 1 showing nanoparticles ranging from 10 to 30nm; the two-dimensional sheet material surface edges are crimped, consistent with common graphene.
FIG. 4 is a high resolution transmission electron micrograph of the product of example 1 showing that the black particles in the transmission electron micrograph actually have a carbon coating on the nanoparticle surface, the coating being about 6-7 graphene layers; the presence of the coated carbon layer contributes to the stability of the magnetic properties of the material, which is otherwise susceptible to reaction with water, oxygen, etc. in the surrounding environment.
FIG. 5 shows the magnetic properties of the product of example 1, with a large hysteresis loop, indicating that the material has a strong magnetic property and retains a high magnetic property after the magnetic field is removed.
Example 2
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 5g urea as raw material, taking 0.05g ferrocene as catalyst, mixing uniformly, loading into a screw thread sealable graphite tank with an internal effective volume of 1000mL in high-purity nitrogen atmosphere (oxygen content of 0%), and stacking to a thickness of 0.05g/cm 2 Sealing, placing in a tube furnace, heating to 1000 ℃ for 10 hours, keeping the temperature constant for 10 minutes, cooling to 500 ℃ at 5 ℃/min, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Example 3
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 0.5g dicyandiamide as a raw material, taking 0.5g nickel dichloride as a catalyst, uniformly mixing, putting the mixture into a sealable stainless steel tank (flange seal, graphite sealing strip) with an internal effective volume of 1000mL in a mixed atmosphere of nitrogen and oxygen (oxygen content of 30%), and stacking the mixture to a thickness of 0.01g/cm 2 Sealing and then placing in a muffle furnace,and 2h, heating to 910 ℃, keeping the temperature for 10h, cooling to 500 ℃ at 10 ℃/min, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Example 4
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 900g cyanuric acid as raw material, using 100g cobaltocene as catalyst, mixing uniformly, placing into a sealable quartz tank with an effective internal volume of 10L in high purity argon atmosphere (oxygen content of 0%), and stacking with a thickness of 1g/cm 2 Sealing, placing in a trolley furnace, heating to 650 ℃ for 1h, keeping the temperature constant for 2h, cooling to 500 ℃ at 1 ℃/min, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Example 5
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 1.5g of thiourea as a raw material, taking 0.5g of ferrocene as a catalyst, uniformly mixing, placing the mixture into a sealable quartz tank with an effective internal volume of 100mL and a stacking thickness of 0.2g/cm in an air atmosphere (oxygen content of 22 percent) 2 Sealing, placing in microwaves, heating to 650 ℃ by microwaves for 5min, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Example 6
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 1.5g melamine as raw material, taking 1.5g ferrocene as catalyst, mixing uniformly, placing into a sealable ceramic tank with an effective internal volume of 100mL and a stacking thickness of 0.1g/cm in an air atmosphere (oxygen content of 22%) 2 Sealing, placing the mixture in microwaves, heating to 1000 ℃ by microwaves, heating for 30 seconds, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Example 7
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 1.5g melamine as raw material, taking 0.5g ferrocene as catalyst, mixing uniformly, placing into a screw thread grinding sealable quartz tank with an effective internal volume of 100mL in air atmosphere (oxygen content of 22%), and stacking to a thickness of 0.2g/cm 2 Sealing, placing in a muffle furnace, heating to 700 ℃ for 2.5h, keeping the temperature constant for 2h, cooling to 500 ℃ at 10 ℃/min, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Example 8
The preparation method of the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nano particles comprises the following steps:
taking 1.5g melamine as raw material, taking 1.5g ferrocene as catalyst, mixing uniformly, placing into a sealable ceramic tank with an effective internal volume of 100mL and a stacking thickness of 0.1g/cm in an air atmosphere (oxygen content of 22%) 2 Sealing, placing in microwaves, heating to 910 ℃ by microwaves, heating for 2min, naturally cooling to room temperature, and taking out the product, namely the carbon-loaded iron oxide nanoparticle nitrogen-doped magnetic graphene.
Claims (5)
1. The preparation method of the carbon-supported magnetic nanoparticle nitrogen-doped magnetic graphene is characterized by comprising the following steps of:
(1) Taking molecules capable of simultaneously providing a carbon source and a nitrogen source as raw materials, taking metallocene as a catalyst, and uniformly mixing to obtain a mixture of the raw materials and the catalyst;
(2) Uniformly dispersing the mixture of the raw materials and the catalyst in a sealable reaction container in an atmosphere with the oxygen content of 0-30%, sealing, then placing the mixture in a reaction device for heat treatment, naturally cooling to room temperature, and taking out the product, namely the carbon-coated magnetic nanoparticle nitrogen-doped magnetic graphene;
the reaction device in the step (2) is an electric furnace and an electromagnetic oven, and when the reaction device is the electric furnace, the specific heat treatment is as follows: raising the temperature to 650-1000 ℃ for 1-10 h, keeping the constant temperature for 10 min-10 h, and lowering the temperature to 500 ℃ by adopting 1-10 ℃/min; when the reaction device is an induction cooker, the specific heat treatment is as follows: heating to 650-1000 ℃ for 30 s-5 min;
the molecules capable of providing the carbon source and the nitrogen source in the step (1) are one or a mixture of more of melamine, urea, thiourea, dicyandiamide and cyanuric acid according to any ratio, and the metallocene is one or a mixture of more of ferrocene, nickel-dicyclopentadienyl or cobalt-dicyclopentadienyl according to any ratio; the mass ratio of the raw materials to the catalyst is 100:1-100.
2. The method for preparing carbon-supported magnetic nanoparticle nitrogen-doped magnetic graphene according to claim 1, wherein the mass-to-volume ratio of the mixture of the raw material and the catalyst in the step (2) to the effective volume inside the sealable reaction vessel is 1-100 g/L, and the stacking thickness of the mixture of the raw material and the catalyst in the sealable reaction vessel is 0.01-1 g/cm 2 。
3. The method for preparing the carbon-coated magnetic nanoparticle nitrogen-doped magnetic graphene according to claim 1, wherein the sealable reaction vessel in the step (2) is cylindrical, the sealable reaction vessel is made of a high-temperature resistant material, and the sealable reaction vessel is sealed by one or a combination of threads, a grinding port, a graphite sealing strip or a flange.
4. The method for preparing the carbon-supported magnetic nanoparticle nitrogen-doped magnetic graphene according to claim 3, wherein the high-temperature resistant material is graphite, stainless steel, ceramic or quartz glass.
5. The method for preparing the nitrogen-doped magnetic graphene carrying the carbon-coated magnetic nanoparticles according to claim 4, wherein the sealable reaction vessel is made of graphite and is performed in an inert protective atmosphere.
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