CN108455565B - Preparation method of nitrogen-doped graphitized nano carbon cage - Google Patents
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Abstract
The invention discloses a preparation method of a nitrogen-doped graphitized carbon nanocage, belonging to the field of novel carbon nanocages. The preparation method comprises the following steps: physically mixing cyanamide compound with metal acetate or metal carbonate to obtain a mixture; carbonizing the mixture under the atmosphere of inert gas to obtain a carbonized product; performing acid etching on the carbonized product to obtain an etched product; and purifying the etching product to obtain the nitrogen-doped graphitized nano carbon cage. The preparation method provided by the embodiment of the invention does not need to prepare a template in advance, thereby simplifying the production process.
Description
Technical Field
The invention relates to the field of novel nano carbon materials, in particular to a preparation method of a nitrogen-doped graphitized nano carbon cage.
Background
Hollow nanocarbon cages are generally produced as a by-product of carbon nanotubes, and the novel carbon-based nanomaterial is a hollow shell-like nanocarbon material formed of a plurality of graphite sheets. The pore diameter of most hollow nano carbon cages is between 2 and 100nm, and the hollow nano carbon cages have large specific surface area, so that the hollow nano carbon cages can be widely applied to the fields of nano reaction containers, adsorbents, electrochemistry and the like.
The existing preparation method of the hollow nano carbon cage mainly comprises a hard template method. The existing method for preparing the hollow nano carbon cage by a hard template method needs to prepare an amorphous carbon precursor with a catalyst, and the preparation method of the amorphous carbon precursor comprises the following steps: introducing a mixed gas of inert gas and acetylene into carbonyl iron liquid at 0 ℃ to carry out catalyst to form reaction gas, introducing the reaction gas into the top of a main reactor, reacting through a high-temperature region, and continuously obtaining an amorphous carbon precursor with uniformly distributed iron catalyst particles in a product collector at the bottom of the main reactor; then preparing a hollow nano carbon cage from the amorphous carbon precursor through heat treatment; and finally removing the residual catalyst to obtain the hollow carbon nanocage.
In the process of implementing the invention, the inventor finds that the prior art has at least the following problems:
when the hollow nano carbon cage is prepared by the hard template method, an amorphous carbon precursor needs to be prepared, and the process for preparing the amorphous carbon precursor is complex, time-consuming and labor-consuming.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a nitrogen-doped graphitized carbon nanocage, which can simply prepare the nitrogen-doped graphitized carbon nanocage. The technical scheme is as follows:
the embodiment of the invention provides a preparation method of a nitrogen-doped graphitized carbon nanocage, which comprises the following steps:
physically mixing cyanamide compound with metal acetate or metal carbonate to obtain a mixture;
carbonizing the mixture under the atmosphere of inert gas to obtain a carbonized product;
performing acid etching on the carbonized product to obtain an etched product;
and purifying the etching product to obtain the nitrogen-doped graphitized nano carbon cage.
Specifically, the mass ratio of the cyanamide compound to the metal acetate or the metal carbonate is (5-20): 1.
Specifically, the cyanamide compound is dicyandiamide or melamine.
Specifically, the metal acetate is calcium acetate, manganese acetate or magnesium acetate.
Specifically, the metal carbonate is calcium carbonate or magnesium carbonate.
Specifically, the carbonization treatment method comprises the following steps: and under the atmosphere of inert gas, heating the mixture from room temperature to 800-1000 ℃ according to the heating rate of 2-5 ℃/min, and then preserving heat for 1-5 h to obtain the carbonized product.
Specifically, the acid etching method comprises the following steps: and (3) placing the carbonized product into a hydrochloric acid solution or a sulfuric acid solution with the concentration of 3-10 mol/L, and reacting for 24-48 h at the temperature of 60-90 ℃ to obtain the etched product.
Specifically, the purification method comprises the following steps: and carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake in water for many times, carrying out suction filtration, collecting filtrate obtained by each suction filtration until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at the temperature of 60-80 ℃ to obtain the nitrogen-doped graphitized carbon nanocage.
Specifically, the mixture is ground prior to the carbonization treatment.
Specifically, the inert gas is nitrogen, argon or helium.
The technical scheme provided by the embodiment of the invention has the following beneficial effects: according to the preparation method of the nitrogen-doped graphitized carbon nanocage provided by the embodiment of the invention, during carbonization treatment, the cyanamide compound reacts with metal acetate or metal carbonate to generate a cyano metal compound, meanwhile, other products decomposed by the cyanamide compound are carbonized to form a nitrogen-containing carbon layer, the carbon layer is deposited and coated on the surface of the cyano metal compound, and the cyano metal compound is simultaneously used as a catalyst and a template agent to perform graphitization catalysis on the coated carbon layer; finally, the cyano-group metal compound is etched away, so that nitrogen-doped graphitized nano carbon cages with cage-shaped structures are left; the preparation provided by the embodiment of the invention does not need to prepare a template, and the production process is simplified.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below with reference to the attached drawings, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a low-power transmission electron microscope image of a nitrogen-doped graphitized nanocarbon cage according to an embodiment of the present invention;
fig. 2 is a high-power transmission electron microscope image of a nitrogen-doped graphitized nanocarbon cage according to an embodiment of the present invention;
fig. 3 is an X-ray photoelectron spectrum of a nitrogen-doped graphitized nanocarbon cage provided by an embodiment of the present invention;
fig. 4 is a low-power transmission electron microscope image of the nitrogen-doped graphitized nanocarbon cage provided in example two of the present invention;
fig. 5 is an X-ray photoelectron spectrum of the nitrogen-doped graphitized nanocarbon cage provided by the second embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
The embodiment of the invention provides a preparation method of a nitrogen-doped graphitized carbon nanocage, which comprises the following steps:
the cyanamide compound and metal acetate or metal carbonate are physically mixed to obtain a mixture.
Carbonizing the mixture under the atmosphere of inert gas to obtain a carbonized product; the carbonized product is a cyano metal compound coated with a carbon layer on the surface.
And carrying out acid etching on the carbonized product to remove the metal compound to obtain an etched product.
And purifying the etching product to obtain the nitrogen-doped graphitized nano carbon cage.
Specifically, the mass ratio of the cyanamide compound to the metal acetate or the metal carbonate can be (5-20): 1.
Specifically, the cyanamide compound may be dicyandiamide or melamine.
Specifically, the metal acetate may be calcium acetate, manganese acetate, or magnesium acetate. In the carbonization process, calcium acetate, manganese acetate or magnesium acetate and cyanamide compounds form cyano metal compounds, and the cyano metal compounds can be completely etched in the acid etching process.
In particular, the metal carbonate may be calcium carbonate or magnesium carbonate. In the carbonization process, the calcium carbonate or magnesium carbonate and the cyanamide compound form a cyano metal compound, and the cyano metal compound can be completely etched in the acid etching process.
Specifically, the method of carbonization treatment may include: and under the atmosphere of inert gas, heating the mixture from room temperature to 800-1000 ℃ according to the heating rate of 2-5 ℃/min, and then preserving heat for 1-5 h to obtain a carbonized product.
Specifically, the acid etching method comprises the following steps: and (3) placing the carbonized product into a hydrochloric acid solution with the concentration of 3-10 mol/L, and reacting for 24-48 h at 80 ℃ to obtain an etching product.
Specifically, the method of purification may include: and carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake in water for a plurality of times, carrying out suction filtration, respectively collecting filtrate until the pH value of the obtained filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 60-80 ℃ to obtain the powdery nitrogen-doped graphitized carbon nanocage.
Specifically, the mixture is ground prior to the carbonization treatment. So that the cyanamide compound and the metal acetate or the metal carbonate in the mixture are mixed more uniformly.
Specifically, the inert gas may be nitrogen, argon, or helium.
Example one
The method comprises the steps of physically mixing dicyandiamide and calcium acetate in a mass ratio of 5:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating from room temperature to 800 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, preserving heat at 800 ℃ for 1h, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding hydrochloric acid solution with the concentration of 3mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 80 ℃ for 24 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 60 ℃ for 24 hours to obtain the nitrogen-doped graphitized nanocarbon cage.
Respectively performing transmission electron microscopy characterization and X-ray photoelectron spectroscopy (XPS) on the nitrogen-doped graphitized carbon nanocage obtained in the first embodiment, wherein the transmission electron microscopy characterization test method comprises the following steps: dispersing nitrogen-doped graphitized nano carbon cages in deionized water, performing ultrasonic dispersion to obtain a mixed solution, sucking a certain amount of the mixed solution by using a liquid-transferring gun, dripping the mixed solution on a clean copper net, placing the copper net under an infrared lamp, drying, and performing transmission electron microscope observation. The result observed by using a low-power transmission electron microscope is shown in fig. 1, and it can be clearly seen from fig. 1 that a plurality of nitrogen-doped graphitized nanocarbon cages are stacked together. The result observed by using a high-power transmission electron microscope is shown in fig. 2, and it can be clearly seen from fig. 2 that the nitrogen-doped graphitized nanocarbon cage has graphitized stripes, which proves that the nitrogen-doped graphitized nanocarbon cage obtained by the embodiment of the present invention is graphitized.
The test method adopting X-ray photoelectron spectroscopy comprises the following steps: the method comprises the steps of flatly paving powdery nitrogen-doped graphitized carbon nanocages on a double-sided adhesive (the length of the double-sided adhesive can be 1cm, and the width of the double-sided adhesive can be 1cm), compacting the nitrogen-doped graphitized carbon nanocages on the double-sided adhesive to avoid powder falling, and then carrying out X-ray photoelectron spectroscopy analysis and test, wherein the result is shown in fig. 3, and fig. 3 shows that the nitrogen-doped graphitized nanocages only have three elements, namely carbon (C), nitrogen (N) and oxygen (O), and no other elements exist, which shows that the obtained nitrogen-doped graphitized nanocages are pure and nitrogen-doped, and according to the calculated peak area ratio, the nitrogen content of the nitrogen-doped graphitized nanocages obtained by the embodiment of the invention can be known to be 8.2 at%.
Example two
Physically mixing melamine and magnesium acetate in a mass ratio of 10:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating from room temperature to 800 ℃ at a heating rate of 2 ℃/min under the protection of helium gas, preserving heat at 800 ℃ for 3h, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding a sulfuric acid solution with the concentration of 5mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 80 ℃ for 48 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 60 ℃ for 24 hours to obtain the nitrogen-doped graphitized carbon nanocage.
And (3) respectively performing transmission electron microscope characterization and X-ray photoelectron spectroscopy analysis on the nitrogen-doped graphitized nano carbon cage obtained in the second embodiment, wherein the transmission electron microscope characterization test method is the same as that of the first embodiment, and the result observed by using a low-magnification transmission electron microscope is shown in fig. 4, and it can be clearly seen from fig. 4 that a plurality of nitrogen-doped graphitized nano carbon cages are stacked together.
The test method using X-ray photoelectron spectroscopy is the same as the first example, and the result is shown in fig. 5, it can be seen from fig. 5 that only three elements, namely carbon (C), nitrogen (N) and oxygen (O), exist in the nitrogen-doped graphitized nanocarbon cage, and no other element exists, which indicates that the obtained nitrogen-doped graphitized nanocarbon cage is pure and nitrogen-doped, and according to the calculated peak area ratio, the nitrogen content of the nitrogen-doped graphitized nanocarbon cage obtained in the example of the present invention is 9.2 at%.
EXAMPLE III
The method comprises the steps of physically mixing dicyandiamide and calcium carbonate in a mass ratio of 10:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating from room temperature to 900 ℃ at a heating rate of 5 ℃/min under the protection of helium atmosphere, preserving heat at 900 ℃ for 3 hours, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding a hydrochloric acid solution with the concentration of 10mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 80 ℃ for 36 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 80 ℃ for 24 hours to obtain the nitrogen-doped graphitized carbon nanocage.
Example four
Physically mixing melamine and calcium acetate in a mass ratio of 10:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating the quartz boat from room temperature to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon atmosphere, preserving the temperature at 800 ℃ for 2h, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding a hydrochloric acid solution with the concentration of 5mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 80 ℃ for 24 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 80 ℃ for 48 hours to obtain the nitrogen-doped graphitized nanocarbon cage.
EXAMPLE five
The method comprises the steps of physically mixing dicyandiamide and manganese acetate in a mass ratio of 20:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating from room temperature to 1000 ℃ at a heating rate of 5 ℃/min under the protection of helium atmosphere, preserving heat at 1000 ℃ for 2 hours, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding a hydrochloric acid solution with the concentration of 10mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 80 ℃ for 48 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 60 ℃ for 48 hours to obtain the nitrogen-doped graphitized carbon nanocage.
EXAMPLE six
Physically mixing melamine and manganese acetate in a mass ratio of 15:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating the quartz boat to 1000 ℃ from room temperature at a heating rate of 2 ℃/min under the protection of helium gas, preserving the temperature at 1000 ℃ for 2h, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding a hydrochloric acid solution with the concentration of 10mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 60 ℃ for 48 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 80 ℃ for 24 hours to obtain the nitrogen-doped graphitized carbon nanocage.
EXAMPLE seven
The method comprises the following steps of physically mixing dicyandiamide and magnesium acetate in a mass ratio of 10:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating the quartz boat from room temperature to 900 ℃ at a heating rate of 5 ℃/min under the protection of helium gas, preserving heat at 900 ℃ for 3 hours, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding hydrochloric acid solution with the concentration of 3mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 80 ℃ for 24 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 60 ℃ for 48 hours to obtain the nitrogen-doped graphitized nanocarbon cage.
Example eight
Physically mixing dicyandiamide and magnesium carbonate in a mass ratio of 5:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating from room temperature to 800 ℃ at a heating rate of 2 ℃/min under the protection of helium atmosphere, preserving heat at 800 ℃ for 3h, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding a hydrochloric acid solution with the concentration of 5mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 80 ℃ for 48 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 60 ℃ for 24 hours to obtain the nitrogen-doped graphitized nanocarbon cage.
Example nine
Physically mixing dicyandiamide and magnesium carbonate in a mass ratio of 5:1 to obtain a mixture, fully grinding the mixture in a mortar, placing the mixture on a quartz boat, placing the quartz boat carrying the mixture in a tube furnace, heating from room temperature to 1000 ℃ at a heating rate of 3 ℃/min under the protection of helium atmosphere, preserving heat at 1000 ℃ for 3h, and cooling to room temperature to obtain a carbonized product (powder). Putting the carbonized product into a round-bottom flask, adding a hydrochloric acid solution with the concentration of 10mol/L into the round-bottom flask, carrying out reflux reaction on the round-bottom flask at 90 ℃ for 48 hours to obtain an etched product, carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake into distilled water for many times, carrying out suction filtration again, respectively collecting filtrates until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at 70 ℃ for 36 hours to obtain the nitrogen-doped graphitized carbon nanocage.
The preparation method provided by the embodiment of the invention adopts a solid-phase chemical reaction to generate a nitrogen-doped graphitized nano carbon cage, during carbonization treatment, cyanamide compounds react with metal acetate or metal carbonate to generate cyano metal compounds, meanwhile, other products decomposed by the cyanamide compounds are carbonized to form a nitrogen-containing carbon layer, the carbon layer is deposited and coated on the surface of the cyano metal compounds, and the cyano metal compounds are simultaneously used as a catalyst and a template agent to perform graphitization catalysis on the coated carbon layer; finally, the cyano-group metal compound is etched away, so that nitrogen-doped graphitized nano carbon cages with cage-shaped structures are left; the preparation method provided by the embodiment of the invention does not need to prepare a template in advance, so that the production process is simplified, and meanwhile, the preparation method has the advantages of low raw material cost and no environmental pollution, and is suitable for industrial large-scale production.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a nitrogen-doped graphitized carbon nanocage is characterized by comprising the following steps:
physically mixing cyanamide compounds and metal acetate or metal carbonate, wherein the cyanamide compounds are dicyandiamide or melamine, and the metal acetate is calcium acetate, manganese acetate or magnesium acetate to obtain a mixture;
carbonizing the mixture under the atmosphere of inert gas to obtain a carbonized product;
performing acid etching on the carbonized product to obtain an etched product;
and purifying the etching product to obtain the nitrogen-doped graphitized nano carbon cage.
2. The production method according to claim 1, wherein the mass ratio of the cyanamide compound to the metal acetate or the metal carbonate is (5-20): 1.
3. The method according to claim 1, wherein the metal carbonate is calcium carbonate or magnesium carbonate.
4. The production method according to claim 1, wherein the carbonization treatment method includes: and under the atmosphere of inert gas, heating the mixture from room temperature to 800-1000 ℃ according to the heating rate of 2-5 ℃/min, and then preserving heat for 1-5 h to obtain the carbonized product.
5. The method of manufacturing according to claim 1, wherein the acid etching method comprises: and (3) placing the carbonized product into a hydrochloric acid solution or a sulfuric acid solution with the concentration of 3-10 mol/L, and reacting for 24-48 h at the temperature of 60-90 ℃ to obtain the etched product.
6. The method of claim 1, wherein the purifying comprises: and carrying out suction filtration on the etched product to obtain a filter cake, repeatedly dispersing the filter cake in water for many times, carrying out suction filtration, collecting filtrate obtained by each suction filtration until the pH value of the filtrate is 6.8-7.2 to obtain a washed filter cake, and drying the washed filter cake at the temperature of 60-80 ℃ to obtain the nitrogen-doped graphitized carbon nanocage.
7. The method according to claim 1, wherein the mixture is ground before the carbonization treatment.
8. The method of claim 1, wherein the inert gas is nitrogen, argon, or helium.
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| CN104518219A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Applications of porous carbon material in lithium-thionyl chloride battery positive electrode |
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