CN111250008B - Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method - Google Patents
Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a hollow sphere nano material assembled by CoFe alloy wrapped in N and P co-doped carbon by a solvent-free thermal hydrolysis method, which comprises the steps of uniformly grinding melamine, ferric oxide and vitamin B12 in an agate mortar, placing the obtained mixed material in a tube furnace, heating to 550 ℃ at the heating rate of 2 ℃/min for 2h in the nitrogen atmosphere, heating to 700 ℃ at the heating rate of 5 ℃/min for 1.5h, naturally cooling to room temperature, soaking the obtained product in 0.5M sulfuric acid solution for 20h, and then sequentially centrifuging, washing and drying to obtain the CoFe @ NP-CHS nano material. The preparation process is simple and convenient, no solvent is used, the prepared material with the hollow sphere structure can obviously improve the catalytic activity of the material on oxygen reduction reaction and oxygen evolution reaction, and the material has excellent performance in the aspect of zinc-air batteries.
Description
Technical Field
The invention belongs to the technical field of synthesis of carbon-based nano materials, and particularly relates to a method for synthesizing a hollow sphere (CoFe @ NP-CHS) nano material which is wrapped in N and P co-doped carbon assembly and is formed by CoFe alloy through a simple solvent-free thermal decomposition method.
Background
Due to the increasing problems of environmental pollution and energy crisis caused by the high dependence on fossil fuels, great interest has been raised in developing renewable and clean energy storage and conversion technologies. Metal-air batteries have attracted extensive attention for their advantages of low cost, environmental friendliness, high theoretical energy density, good safety, and the like. However, the large overpotential and slow kinetics of electrochemical reactions severely limit the large-scale implementation of these devices.
Recently, carbon materials doped with heteroatoms (such as N and P) are considered as promising catalysts for replacing noble metal catalysts due to the advantages of highly adjustable structure and composition, excellent stability and easy preparation. In particular, due to the strong electron donating ability and large electronegativity between N and P, implantation of N and P atoms into a carbon lattice will impart a more positive charge density to adjacent carbon atoms, accelerating electron transfer, promoting O2Adsorption of molecules further improves catalytic performance.
The transition metal (M = Ni, Fe, Co, etc.) and the alloy thereof are doped into the carbon matrix, so that the available active sites are increased, the electronic structure of the carbon material is adjusted, and the catalytic activity is improved. Meanwhile, metal Nanoparticles (NPs) are coated in the carbon skeleton, so that the stability of the material is further improved, and the NPs are prevented from agglomerating in the test.
In addition to chemical composition, structure also has a very large influence on catalytic activity. In general, a large specific surface area and porous structure can expose sufficient active sites and provide charge transfer channels to accelerate mass transport between the catalyst and the electrolyte. Therefore, designing heteroatom and metal alloy doped carbon materials with tunable structures remains a great challenge. In response to this problem, researchers have prepared carbon materials (nanofibers, nanocubes) having morphology by various methods including hydrothermal method, electrospinning method, pyrolysis method, sacrificial template method, and the like. However, these methods generally involve organic solvents, are constructed in multiple steps, and the materials are prone to collapse and sinter during the preparation process, so that the preparation of hollow spheres by a simple solvent-free pyrolysis method is a hot spot of current research.
Disclosure of Invention
The invention provides a method for synthesizing a CoFe alloy wrapped N, P co-doped carbon assembled hollow sphere (CoFe @ NP-CHS) nano material by a solvent-free thermal decomposition method, which has a simple preparation process and is used for overcoming the problems existing in the multi-step synthesis of hollow sphere carbon materials in the prior art.
The invention adopts the following technical scheme for solving the technical problems, and the method for synthesizing the hollow sphere nano material assembled by coating the CoFe alloy on N and P co-doped carbon by a solvent-free thermal decomposition method is characterized by comprising the following specific steps of: mixing melamine and ferric oxide (Fe)2O3) And vitamin B12 (VB 12) are uniformly ground in an agate mortar, wherein the mass ratio of melamine to ferric oxide to vitamin B12 is 10:4:3, the obtained mixed material is placed in a tube furnace, the temperature is increased to 550 ℃ at the heating rate of 2 ℃/min and is kept for 2h in the nitrogen atmosphere, the temperature is increased to 700 ℃ at the heating rate of 5 ℃/min and is kept for 1.5h, then the obtained product is soaked in 0.5M sulfuric acid solution for 20h after being naturally cooled to room temperature, and then the product is sequentially centrifuged, washed and dried to obtain the CoFe alloy coated hollow sphere structure CoFe NP-CHS nano material assembled by N and P co-doped carbon.
The preparation method of the hollow sphere nano material assembled by wrapping the CoFe alloy in N and P co-doped carbon is characterized in that the specific process of forming the hollow sphere nano material is as follows: in the initial stage of the reaction, melamine decomposes to graphite phase carbon nitride (g-C)3N4) With the continuous increase of temperature, vitamin B12 is converted into Co3+And corrin ring, then Co3+Quilt g-C3N4Reduction to Co atoms with Fe2O3As hard templates and iron sources, g-C3N4Derivative cyano fragment and corrin ring as C, N and P source to form N, P codoped carbon layer wrapped in Fe2O3Co atoms and Fe species nucleate to form CoFe alloy nanoparticles further embedded in the carbon substrate, and after the temperature drops to room temperature, the product is immersed in a 0.5M sulfuric acid solution for 20h to remove Fe2O3The number of the templates is set to be,the CoFe @ NP-CHS nano material with the hollow sphere structure can remarkably improve catalytic activity on Oxygen Reduction Reaction (ORR) and hydrogen evolution reaction (OER), and meanwhile, the CoFe @ NP-CHS nano material with the hollow sphere structure has good charge and discharge performance and charge and discharge cycle stability when used for a zinc-air battery.
Compared with the prior art, the invention has the following advantages: the hollow sphere nano material which is wrapped by the CoFe alloy and is assembled by N and P co-doped carbon is prepared by a simple solvent-free thermal decomposition method, the preparation process is simple and convenient, compared with other carbon hollow sphere nano materials, the hollow sphere structure of the CoFe @ NP-CHS nano material prepared by the invention can obviously improve the catalytic activity of the CoFe @ NP-CHS nano material on Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER), and the CoFe NP @ CHS nano material has excellent performance in the aspect of a zinc-air battery.
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FIG. 1 is a scanning electron microscope image and a transmission electron microscope image of a CoFe @ NP-CHS nano material;
FIG. 2 is a schematic diagram of the formation process of CoFe @ NP-CHS nanomaterial;
FIG. 3 shows (A) the LSV curves of CoFe @ NP-CHS nanomaterial and control material at different temperatures and Pt/C in 0.1M KOH solution at 1600rpm with 10mV/s sweep, (B) Tafel slope, (C) the LSV curves of CoFe @ NP-CHS nanomaterial at different rotation speeds, and (D) the K-L plot;
FIG. 4 (A) CoFe @ NP-CHS nanomaterial and control material and RuO at different temperatures2LSV curve in 1M KOH solution at 1600rpm with sweep rate of 5mV/s, (B) Tafel slope (C) OER polarization plots of CoFe @ NP-CHS nanomaterials before and after 2000 cycles in 1M KOH solution, (D) current density of 10mA cm-2Chronopotentiometric plot of the lower catalyst;
in FIG. 5, (A) open circuit voltage of air cell based on CoFe @ NP-CHS nanomaterial, (B) two zinc-air cells connected in series based on CoFe @ NP-CHS nanomaterial for illuminating light emitting diode (3V), (C) charge-discharge polarization curve, (D) polarization curve and power density curve(E) at a current density of 10mA cm-2Long-term constant-current charge-discharge cycle curve.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Reagent and instrument
Melamine, vitamin B12 (VB 12) and ferric oxide (Fe)2O3) Ethanol and sulfuric acid were purchased from Shanghai chemical plant, and all reagents were analytically pure. Scanning electron microscope (SEM, JSM-6390LV, JEOL, Japan), transmission electron microscope (TEM, JEM-2100, JEOL, Japan), acceleration voltage was 200 kV. The chemical composition and crystalline phase structure of the CoFe @ NP-CHS nanomaterial were determined by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. Raman spectroscopy (Renishaw 1000 spectrometer) was used to analyze the defects and graphitization degree of the material. Thermogravimetric analysis (TGA) was performed in air on a Netzsch STA 449C thermogravimetric analyzer.
Mixing melamine and Fe2O3And VB12 are uniformly ground in an agate mortar, wherein melamine and Fe are contained2O3And the mass ratio of the obtained mixed material to VB12 is 10:4:3, the obtained mixed material is placed in a tubular furnace, the temperature is raised to 550 ℃ at the heating rate of 2 ℃/min and is kept for 2h in the nitrogen atmosphere, the temperature is raised to 700 ℃ at the heating rate of 5 ℃/min and is kept for 1.5h, then the obtained product is naturally cooled to room temperature, the obtained product is soaked in 0.5M sulfuric acid solution for 20h, and then the obtained product is sequentially centrifuged, washed and dried to obtain the CoFe alloy wrapped N, P-codoped carbon assembled hollow sphere structure CoFe NP @ CHS nano material.
FIG. 1 is a scanning electron microscope image and a transmission electron microscope image of a CoFe @ NP-CHS nano material. As shown in the figure 1, the structure of the CoFe @ NP-CHS nano material is composed of a plurality of hollow spheres with cracks, so that the active area of the material can be enlarged, and the electron transmission is facilitated, and the catalytic efficiency is improved. As can be seen from B-D in FIG. 1, the nanoparticles wrapped in the carbon layer correspond to CoFe alloy, demonstrating the successful preparation of CoFe @ NP-CHS nanomaterials.
As shown in fig. 2, the growth mechanism of CoFe @ NP-CHS nanomaterials is demonstrated, which can be explained as a two-step growth mechanism: pyrolysis and etching. According to the relevant literature, melamine decomposes to g-C during the course of the reaction3N4. As the temperature continued to rise, VB12 was converted to Co3+And corrin ring, then Co3+Quilt g-C3N4Reduced to Co atoms. At the same time, Fe2O3As a hard template and iron source. g-C3N4Derivative cyano fragment and corrin ring as C, N and P source to form N, P codoped carbon layer wrapped in Fe2O3Of (2) is provided. The Co atoms and Fe species nucleate to form CoFe alloy nanoparticles, which are further embedded in the carbon substrate. After the temperature had dropped to room temperature, the product was immersed in a 0.5M sulfuric acid solution for 20 hours to remove Fe as much as possible2O3And finally obtaining the CoFe alloy wrapped N, P co-doped carbon assembled hollow sphere structure CoFe @ NP-CHS nano material.
FIGS. 3-4 are catalytic applications of CoFe @ NP-CHS nanomaterials on ORR and OER under basic conditions. FIG. 3A is a linear scanning voltammogram of CoFe @ NP-CHS nanomaterials in 0.1M KOH solutions. Half-wave potential of CoFe @ NP-CHS nanomaterial (E 1/20.86V) was more positive than the other control materials CoFe @ NPC-600 (0.64V), CoFe @ NPC-800 (0.85V) and Pt/C (0.84V), indicating that the material had the best ORR catalytic performance. Tafel slope (81.5 mV dec) for CoFe @ NP-CHS nanomaterials as shown by Tafel slope in FIG. 3B-1) Are all smaller than the control material CoFe @ NPC-600 (140.1 mV dec)-1），CoFe@NPC-800（98.2mV dec-1) And Pt/C (93.1 mV dec)-1) This demonstrates the faster reaction kinetics of CoFe @ NP-CHS nanomaterials during the reaction process. FIGS. 3C-D show LSV curves of CoFe @ NP-CHS nanomaterials at different rotation speeds and corresponding K-L equations, and the electron transfer number of CoFe @ NP-CHS is calculated to be about 4 from the slope of the K-L equations, which further proves the electron transfer process of the CoFe @ NP-CHS nanomaterials.
FIG. 4A is the LSV curves of the OER in 1M KOH solution for CoFe @ NP-CHS nanomaterials and other controls. As can be seen from the graph, the current density was 10mA cm-2Overpotential (302 mV) and RuO of CoFe @ NP-CHS nano material2(270 mV) is comparable but less than the other control materials CoFe @ NPC-600 (348 mV) and CoFe @ NPC-800 (329 mV), which further demonstrates that the CoFe @ NP-CHS nanomaterial has excellent OER catalytic capability. FIG. 4B shows the Tafel slope (92.3 mV dec) for CoFe @ NP-CHS nanomaterials-1) Ratio CoFe @ NPC-600 (118.2 mV dec)-1），CoFe@NPC-800（92.29mV dec-1) And RuO2（130.3mV dec-1) Further confirming the favorable kinetics of CoFe @ NP-CHS. FIGS. 4C-D show the stability of CoFe @ NP-CHS. In FIG. 4C, the CoFe @ NP-CHS nanomaterial shows a small change in current after 2000 LSV scans. At the same time, as shown in FIG. 4D, at 10mA cm-2After 7h of timed potential test, the overpotential of the CoFe @ NP-CHS nano material is kept stable, and RuO2The overpotential of the nano material is obviously increased, and the outstanding stability of the CoFe @ NP-CHS nano material is further proved.
FIG. 5 shows the application of CoFe @ NP-CHS nano material in zinc-air batteries. FIG. 5A shows that the CoFe @ NP-CHS nanomaterial has an open circuit voltage of 1.516V. The zinc-air battery assembled by the two CoFe @ NP-CHS nano materials is connected in series, so that a 3V light-emitting diode can be lightened (figure 5B), and the battery assembled by the CoFe @ NP-CHS nano materials has a good practical application prospect. As can be seen from the charging and discharging curves of FIG. 5C, the charging and discharging potential difference ratio Pt/C + RuO of CoFe @ NP-CHS is equal to that of the CoFe @ NP-CHS under the same current density2And small, the CoFe @ NP-CHS nano material has better charge and discharge performance. FIG. 5D is the discharge curve and power density of CoFe @ NP-CHS nanomaterial, where the power density of CoFe @ NP-CHS nanomaterial (123.1 mW cm)-2) Greater than Pt/C + RuO2（43.2mW cm-2) The CoFe @ NP-CHS nano material is shown to have excellent discharge performance. FIG. 5E is at 10mA cm-2And testing the charge-discharge cycle stability of the lower material. After the charge-discharge cycle is carried out for 40 hours, the charge-discharge potential difference of the CoFe @ NP-CHS nano material is basically unchanged, and the Pt/C + RuO2The potential difference between charge and discharge is obviously increasedAnd additionally, the CoFe @ NP-CHS nano material is proved to have excellent charge and discharge stability.
Example 2
In this example, the pyrolysis temperatures (700 ℃ and 900 ℃) were changed, and other experimental conditions were maintained unchanged with reference to example 1, and the prepared CoFe @ NPC-600 and CoFe @ NPC-800 were shown in the support material, the CoFe @ NPC-600 exhibited a blocky morphology, and the disorder characteristic of the carbon substrate, attributable to an insufficient degree of graphitization caused by a low temperature, was seen from the TEM image. In contrast, CoFe @ NPC-800 has a stacked morphology due to collapse and sintering of hollow spheres due to excessive temperatures.
According to the examples 1-2, the pyrolysis temperature is crucial in the process of generating the hollow sphere structure CoFe @ NP-CHS nano material.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (2)
1. The method for synthesizing the hollow sphere nano material assembled by wrapping the CoFe alloy in N and P co-doped carbon by a solvent-free thermal decomposition method is characterized by comprising the following specific steps of: uniformly grinding melamine, ferric oxide and vitamin B12 in an agate mortar, wherein the mass ratio of the melamine to the ferric oxide to the vitamin B12 is 10:4:3, placing the obtained mixed material in a tubular furnace, heating to 550 ℃ at the heating rate of 2 ℃/min for 2h in the nitrogen atmosphere, heating to 700 ℃ at the heating rate of 5 ℃/min for 1.5h, naturally cooling to room temperature, soaking the obtained product in 0.5M sulfuric acid solution for 20h, and then sequentially centrifuging, washing and drying to obtain the CoFe alloy wrapped N, P-codoped carbon assembled hollow sphere structure CoFe NP-CHS nano material.
2. The method of claim 1The method for synthesizing the hollow sphere nano material assembled by wrapping the CoFe alloy in N and P co-doped carbon by the solvent-free thermal decomposition method is characterized in that the specific process for forming the hollow sphere nano material is as follows: in the initial stage of the reaction, melamine decomposes to graphite phase carbon nitride g-C3N4With the continuous increase of temperature, vitamin B12 is converted into Co3+And corrin ring, then Co3+Quilt g-C3N4Reduction to Co atoms with Fe2O3As hard templates and iron sources, g-C3N4Derivative cyano fragment and corrin ring as C, N and P source to form N, P codoped carbon layer wrapped in Fe2O3Co atoms and Fe species nucleate to form CoFe alloy nanoparticles further embedded in the carbon substrate, and after the temperature drops to room temperature, the product is immersed in a 0.5M sulfuric acid solution for 20h to remove Fe2O3The CoFe @ NP-CHS nano material with the hollow sphere structure can remarkably improve catalytic activity on oxygen reduction reaction and hydrogen evolution reaction, and meanwhile, the CoFe @ NP-CHS nano material with the hollow sphere structure has good charge and discharge performance and charge and discharge cycle stability when used for a zinc-air battery.
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| CN111933961B (en) * | 2020-08-19 | 2022-01-18 | 哈尔滨工业大学（深圳） | Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof |
| CN112751048A (en) * | 2021-01-16 | 2021-05-04 | 大连理工大学 | Iron-containing self-loading nitrogen-doped carbon nanotube oxygen reduction catalyst, preparation method and application |
| CN112751047A (en) * | 2021-01-16 | 2021-05-04 | 大连理工大学 | Iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst, preparation method and application |
| CN115224289A (en) * | 2021-04-19 | 2022-10-21 | 安庆北化大科技园有限公司 | Solvent-free grinding preparation method of carbon material coated with nano metal particles and prepared carbon material |
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