CN110980715A - Preparation method of nitrogen-cobalt co-doped graphene material based on 4-amino-1, 2, 4-triazole-5-keto cobalt salt - Google Patents

Preparation method of nitrogen-cobalt co-doped graphene material based on 4-amino-1, 2, 4-triazole-5-keto cobalt salt Download PDF

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CN110980715A
CN110980715A CN201911361870.0A CN201911361870A CN110980715A CN 110980715 A CN110980715 A CN 110980715A CN 201911361870 A CN201911361870 A CN 201911361870A CN 110980715 A CN110980715 A CN 110980715A
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amino
triazole
graphene
cobalt
cobalt salt
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朱佳平
吴铛
林若鹏
杨晓琳
方佳怡
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Guangdong University of Petrochemical Technology
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Guangdong University of Petrochemical Technology
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Abstract

The invention discloses a preparation method of a nitrogen-cobalt co-doped graphene material based on 4-amino-1, 2, 4-triazole-5-ketone cobalt salt, which comprises the steps of dispersing graphene in deionized water, adding an aqueous solution of the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, drying to obtain a graphene-coated 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic, grinding into powder, and heating in a tubular furnace at 500-800 ℃ for 3-5 h to obtain the nitrogen-cobalt co-doped graphene material. Graphene in the obtained graphene material is uniformly coated on the surface of the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt crystal is completely maintained.

Description

Preparation method of nitrogen-cobalt co-doped graphene material based on 4-amino-1, 2, 4-triazole-5-keto cobalt salt
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a nitrogen-cobalt co-doped graphene material based on 4-amino-1, 2, 4-triazole-5-keto cobalt salt.
Background
Graphene (G) is a two-dimensional honeycomb lattice material formed by closely bonding planar single-layer carbon atoms, has a thickness of about 0.35nm, and is the thinnest two-dimensional material in the world.
The electrons of the graphene pass through the graphene without any resistance, the generated heat is less, the conductive efficiency is high, the graphene is the material with the best known conductive performance, and the graphene has unique performance, for example, the tensile strength can reach 130 GPa; the carrier mobility can reach 15000-2Vs (square centimeter per volt-second), which can be more than 10 times that of a silicon wafer; the thermal conductivity can reach 5000W/mK (watt per milli heat conductivity coefficient), which is 3 times of that of diamond; it also has the special properties of room-temperature quantum Hall effect and room-temperature ferromagnetism.
However, graphene has no band gap, its conductivity cannot be controlled as in a conventional semiconductor, and its surface is smooth and inert, which is not conducive to compounding with other materials. The above disadvantages limit the applications of graphene.
Disclosure of Invention
The invention provides a preparation method of a nitrogen-cobalt co-doped graphene material based on a 4-amino-1, 2, 4-triazole-5-keto cobalt salt, and aims to solve the problem that the application is limited because the graphene material is not easily compounded with other materials.
The invention provides a preparation method of a nitrogen-cobalt co-doped graphene material based on a 4-amino-1, 2, 4-triazole-5-keto cobalt salt, which comprises the following steps: dispersing graphene in deionized water, adding an aqueous solution of 4-amino-1, 2, 4-triazole-5-ketone cobalt salt, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, drying to obtain a graphene-coated 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic, grinding the eutectic into powder, and heating in a tubular furnace at 500-800 ℃ for 3-5 h to obtain a nitrogen/cobalt co-doped graphene material; the mass ratio of the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt in the aqueous solution of the graphene and the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt is 1: 1-10.
Preferably, the number of graphene layers is 1 to 2, and the sheet diameter is 0.2 to 100 μm.
Preferably, the mass ratio of the graphene to the 4-amino-1, 2, 4-triazole-5-one cobalt salt is 1: 4-8.
Preferably, the concentration of the 4-amino-1, 2, 4-triazol-5-one cobalt salt in the 4-amino-1, 2, 4-triazol-5-one cobalt salt aqueous solution is 1 to 5 mg/mL.
Preferably, the heating temperature of the tube furnace is set to 600 ℃ and the heating time is 4 h.
In the above, the graphene aqueous dispersion is prepared by the following method: adding graphene into deionized water, stirring for 30-90 min, and ultrasonically shaking for 30-60 min, wherein the mass ratio of the graphene to the deionized water is 1: 20-30.
According to the preparation method of the nitrogen-doped graphene material, provided by the invention, 4-amino-1, 2, 4-triazole-5-keto cobalt salt is reacted with graphene to obtain the graphene material with high nitrogen doping content. In the material, graphene is uniformly coated on the surface of the 4-amino-1, 2, 4-triazole-5-one cobalt salt crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the amino triazolone cobalt salt crystal is completely maintained. By the heat released during the thermal cracking of 4-amino-1, 2, 4-triazol-5-one cobalt salts and by the release of N2The free radicals further open the energy band gap and C-C bond of the graphene, adjust the conductivity type and change the electronic structure; the density of free carriers is improved, and the conductivity and stability are improved; the introduction of the functional group containing nitrogen increases the active sites of the metal particles adsorbed on the surface, enhances the interaction between the metal particles and the graphene, and expands the application of the graphene.
Drawings
Fig. 1 is a scanning electron microscope test chart of the nitrogen-doped graphene material prepared in embodiment 1 of the present invention.
Fig. 2 is an X-ray photoelectron spectroscopy test chart of the nitrogen-doped graphene material prepared in example 1 of the present invention.
Fig. 3 is an X-ray photoelectron spectroscopy test chart of the nitrogen-doped graphene material N1s prepared in example 1 of the present invention.
Fig. 4 is an X-ray photoelectron spectroscopy test chart of C1s of the nitrogen-doped graphene material prepared in example 1 of the present invention.
FIG. 5 shows Co2p of the nitrogen-doped graphene material prepared in example 1 of the present invention1The test chart of X-ray photoelectron spectroscopy.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 0.1g of graphene with the sheet diameter of 100 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 60 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (3) dissolving 0.4 g of 4-amino-1, 2, 4-triazole-5-ketone cobalt salt into 25ml of deionized water, adding the graphene solution, heating at 100 ℃ for 30min, cooling to 0 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic.
Grinding the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic substance coated with graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the doped graphene material with the nitrogen content of 4.06% and the cobalt content of 1.02%.
Example 2
Adding 0.1g of graphene with the sheet diameter of 100 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.2g of 4-amino-1, 2, 4-triazole-5-ketone cobalt salt into 25ml of deionized water, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic.
Grinding the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic substance coated with graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the doped graphene material with the nitrogen content of 2.55% and the cobalt content of 0.82%.
Example 3
Adding 0.1g of graphene with the sheet diameter of 100 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.1g of 4-amino-1, 2, 4-triazole-5-ketone cobalt salt into 25ml of deionized water, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic.
Grinding the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic substance coated with graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the doped graphene material with the nitrogen content of 1.55% and the cobalt content of 0.56%.
Example 4
Adding 0.1g of graphene with the sheet diameter of 100 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.8g of 4-amino-1, 2, 4-triazole-5-ketone cobalt salt into 25ml of deionized water, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 0 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic.
Grinding the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic substance coated with graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the doped graphene material with the nitrogen content of 4.95% and the cobalt content of 0.73%.
Scanning electron microscope tests are performed on the nitrogen-doped graphene material prepared in example 1, and as shown in fig. 1, fig. 1 shows a scanning electron microscope test chart of the nitrogen-doped graphene material prepared in example 1. As shown in the figure 1, graphene in the material is uniformly coated on the surface of the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt crystal, and additives such as an adhesive are not needed, so that the surface performance of the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt crystal is completely maintained.
The nitrogen-doped graphene material and the non-nitrogen-doped graphene material prepared in example 1 were subjected to X-ray photoelectron spectroscopy. As shown in FIG. 2, it can be seen from FIG. 2 that a peak appears in the binding energy at 398-403eV, which indicates that the 4-amino-1, 2, 4-triazol-5-one cobalt salt as a nitrogen source can be effectively combined with graphene to obtain nitrogen-doped graphene.
Further, X-ray photoelectron spectroscopy analysis was performed on N1s of nitrogen-doped graphene, and as shown in fig. 3, pyridine type N, pyrrole type N, graphite type N, and pyridine N oxide appeared at 398.4, 400.1, 401.2, and 402.4eV, respectively.
Further, X-ray photoelectron spectroscopy analysis was performed on C1s of nitrogen-doped graphene, and as shown in fig. 4, C-C, C-N and C ═ O (C ═ N) bonds appeared at 284.5, 285.5, and 287.8 eV, respectively, indicating that 4-amino-1, 2, 4-triazol-5-one cobalt salt as a nitrogen source for preparing nitrogen-doped graphene acted on the mechanism of graphene.
Further, by performing X-ray photoelectron spectroscopy analysis on Co2p of cobalt-doped graphene, as shown in fig. 5, Co Ntv Ox and Co2p appeared at 781.0 and 779.2 eV, respectively, which indicates that 4-amino-1, 2, 4-triazol-5-one cobalt salt as a nitrogen source for preparing nitrogen/cobalt-doped graphene has an effect on the mechanism of graphene.
Combining the above tests, it was demonstrated that 4-amino-1, 2, 4-triazol-5-one cobalt salt as nitrogen source doped with graphene is feasible.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (6)

1. A preparation method of a nitrogen-cobalt co-doped graphene material based on a 4-amino-1, 2, 4-triazole-5-ketone cobalt salt is characterized by comprising the following steps: dispersing graphene in deionized water, adding an aqueous solution of 4-amino-1, 2, 4-triazole-5-ketone cobalt salt, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, drying to obtain a graphene-coated 4-amino-1, 2, 4-triazole-5-ketone cobalt salt eutectic, grinding the eutectic into powder, and heating in a tubular furnace at 500-800 ℃ for 3-5 h to obtain a nitrogen-cobalt co-doped graphene material; the mass ratio of the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt in the aqueous solution of the graphene and the 4-amino-1, 2, 4-triazole-5-ketone cobalt salt is 1: 1-10.
2. The preparation method of the nitrogen-cobalt co-doped graphene material based on the 4-amino-1, 2, 4-triazole-5-keto cobalt salt according to claim 1, wherein the number of graphene layers is 1-2, and the sheet diameter is 0.2-100 μm.
3. The preparation method of the 4-amino-1, 2, 4-triazole-5-one cobalt salt-based nitrogen-cobalt co-doped graphene material according to claim 1, wherein the mass ratio of graphene to 4-amino-1, 2, 4-triazole-5-one cobalt salt is 1: 4-8.
4. The preparation method of the nitrogen-cobalt co-doped graphene material based on the 4-amino-1, 2, 4-triazole-5-one cobalt salt according to claim 1, wherein the concentration of the 4-amino-1, 2, 4-triazole-5-one cobalt salt in the aqueous solution of the 4-amino-1, 2, 4-triazole-5-one cobalt salt is 1-5 mg/mL.
5. The preparation method of the nitrogen-cobalt co-doped graphene material based on the 4-amino-1, 2, 4-triazole-5-keto cobalt salt according to claim 1, wherein the heating temperature of the tubular furnace is set to 600 ℃, and the heating time is 4 hours.
6. The preparation method of the nitrogen-cobalt co-doped graphene material based on the 4-amino-1, 2, 4-triazole-5-keto cobalt salt according to claim 1, wherein the aqueous graphene dispersion is prepared by the following method: adding graphene into deionized water, stirring for 30-90 min, and ultrasonically shaking for 30-60 min, wherein the mass ratio of the graphene to the deionized water is 1: 20-30.
CN201911361870.0A 2019-12-26 2019-12-26 Preparation method of nitrogen-cobalt co-doped graphene material based on 4-amino-1, 2, 4-triazole-5-keto cobalt salt Withdrawn CN110980715A (en)

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Publication number Priority date Publication date Assignee Title
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CN110479340A (en) * 2018-05-14 2019-11-22 南京理工大学 A kind of nanometer cobalt/nitrogen-doped graphene composite material and preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101037A (en) * 2017-12-23 2018-06-01 深圳大学 A kind of preparation method of the nitrogen-doped graphene material based on diamino azo furazan
CN110479340A (en) * 2018-05-14 2019-11-22 南京理工大学 A kind of nanometer cobalt/nitrogen-doped graphene composite material and preparation method

Non-Patent Citations (4)

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Application publication date: 20200410