CN110980713A - Preparation method of graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt - Google Patents
Preparation method of graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt Download PDFInfo
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- CN110980713A CN110980713A CN201911360900.6A CN201911360900A CN110980713A CN 110980713 A CN110980713 A CN 110980713A CN 201911360900 A CN201911360900 A CN 201911360900A CN 110980713 A CN110980713 A CN 110980713A
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Abstract
The invention discloses a preparation method of a graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt, which comprises the steps of dispersing graphene in deionized water, adding an aqueous solution of 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, drying to obtain a graphene-coated 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic, grinding the eutectic into powder, and heating in a tubular furnace at 500-800 ℃ for 3-5 h to obtain the nitrogen-cobalt co-doped graphene material. In the material obtained by the invention, graphene is uniformly coated on the surface of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt crystal is completely maintained.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole 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 graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt, and aims to solve the problem that the graphene material is not easy to be compounded with other materials, so that the application is limited.
The invention provides a preparation method of a graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt, which comprises the following steps: dispersing graphene in deionized water, adding an aqueous solution of 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, drying to obtain a graphene-coated 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic, grinding the eutectic into powder, and placing the powder in a tubular furnace to heat at 500-800 ℃ for 3-5 h to obtain a nitrogen/cobalt co-doped graphene material; wherein the mass ratio of the graphene to the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt in the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt aqueous solution 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 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is 1: 4-8.
Preferably, the concentration of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt in the aqueous solution of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt 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, 5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is used for reacting with graphene, so that the graphene material with high nitrogen doping content is obtained. In the material, graphene is uniformly coated on the surface of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the diamino-bis-triazole crystal is completely maintained. By the heat released during thermal cracking of 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt 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 is an X-ray photoelectron spectroscopy test chart of Co2p of the nitrogen-doped graphene material prepared in example 1 of the present invention.
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, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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) melting 0.4 g of 5,5 '-diamino-3, 3' -1,2, 4-triazole 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 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic crystal coated by graphene.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic substance coated by the graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the co-doped graphene material with the nitrogen content of 15.7% and the cobalt content of 0.87%.
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 (3) melting 0.2g of 5,5 '-diamino-3, 3' -1,2, 4-triazole 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 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic crystal coated by graphene.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic substance coated by the graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the co-doped graphene material with the nitrogen content of 12.4% and the cobalt content of 0.56%.
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 (3) melting 0.1g of 5,5 '-diamino-3, 3' -1,2, 4-triazole 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 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic crystal coated by graphene.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole 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 8.19% and the cobalt content of 0.53%.
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 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt 0.8g 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 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole 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 15.5% and the cobalt content of 0.82%.
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 figure 1, graphene in the material is uniformly coated on the surface of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the 5,5 '-diamino-3, 3' -1,2, 4-triazole 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-.
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, 401.4, and 402.8eV, 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, C-O and C ═ O/C ═ N bonds appeared at 284.5, 285.4, 286.6 and 289.2 eV, respectively, indicating that 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt as a nitrogen source acts on the mechanism for preparing nitrogen-doped graphene.
Further, when X-ray photoelectron spectroscopy was performed on Co2p of nitrogen-doped graphene, as shown in fig. 5, CoO, Co Ntv Ox and Co2p appeared at 779.2, 780.9 and 793.7 eV, respectively1The description shows that 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is used as a nitrogen source to prepare nitrogen-doped graphene, and the nitrogen-doped graphene plays a role in a mechanism of graphene.
Combining the above tests, it was demonstrated that 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is feasible as a nitrogen source to dope graphene.
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 graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is characterized by comprising the following steps: dispersing graphene in deionized water, adding an aqueous solution of 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, drying to obtain a graphene-coated 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt eutectic, grinding into powder, and placing in a tubular furnace to heat at 500-800 ℃ for 3-5 h to obtain a nitrogen-cobalt co-doped graphene material; wherein the mass ratio of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt in the aqueous solution of the graphene and the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is 1: 1-10.
2. The preparation method of the graphene material based on the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt as claimed in 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 graphene material based on the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt as claimed in claim 1, wherein the mass ratio of the graphene to the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is 1: 4-8.
4. The preparation method of the graphene material based on the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt as claimed in claim 1, wherein the concentration of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt in the aqueous solution of the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt is 1-5 mg/mL.
5. The preparation method of the graphene material based on the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt, according to the claim 1, is characterized in that the heating temperature of the tube furnace is set to be 600 ℃, and the heating time is 4 h.
6. The preparation method of the graphene material based on the 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt as the claim 1, is characterized in that the aqueous dispersion of the graphene adopts 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.
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Citations (2)
| 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 |
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| 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)
| Title |
|---|
| B. GRZYB ET AL.: "Guanidine, amitrole and imidazole as nitrogen dopants for the synthesis of N-graphenes", 《RSC ADV.》 * |
| JINGSHUAI YANG ET AL.: "Novel composite membranes of triazole modified graphene oxide and polybenzimidazole for high temperature polymer electrolyte membrane fuel cell applications", 《RSC ADV.》 * |
| SHUJUN CHAO ET AL.: "3,5-Diamino-1,2,4-triazole as a Nitrogen precursor to synthesize highly efficient Co-N/C non-precious metal bifunctional catalyst for oxygen reduction reaction and oxygen evolution reaction", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| YONGFENG LI ET AL.: "Advanced oxygen reduction reaction catalyst based on nitrogen and sulfur co-doped graphene in alkaline medium", 《PHYS.CHEM.CHEM.PHYS.》 * |
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