CN110148763B - Preparation method and application of Fe-doped Mn3O4 carbon-nitrogen material with hollow nano-framework structure - Google Patents

Preparation method and application of Fe-doped Mn3O4 carbon-nitrogen material with hollow nano-framework structure Download PDF

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CN110148763B
CN110148763B CN201910333446.9A CN201910333446A CN110148763B CN 110148763 B CN110148763 B CN 110148763B CN 201910333446 A CN201910333446 A CN 201910333446A CN 110148763 B CN110148763 B CN 110148763B
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徐林
李同飞
刘坤豪
李鑫
刘千玉
李苏霖
孙冬梅
唐亚文
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Abstract

The invention discloses Fe-doped Mn with a hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material and the application thereof in oxygen reduction reaction and zinc-air batteries comprises the following steps: 1) preparation of Fe (CN)6 3‑PVP solution and Mn2+A solution; 2) mixing said Fe (CN)6 3‑PVP solution and Mn2+The solution was mixed well and allowed to stand to give KMnFe (CN)6Precipitating the earthy yellow Prussian blue analogue; 3) mixing the KMnFe (CN)6Washing the solid powder in NaOH solution by alkali, and performing heat treatment in inert atmosphere at the temperature of 250-350 ℃ by temperature programming to obtain the Fe-doped Mn with the hollow nano-framework structure3O4A carbon nitrogen material. The preparation method is low in cost, simple and universal, the prepared material has an open hollow nano-framework structure, can be used as an oxygen reduction reaction electro-catalysis material, has high activity and excellent stability, and can be used as an anode material of a zinc-air battery.

Description

Fe-doped Mn with hollow nano-framework structure3O4Preparation method and application of carbon and nitrogen material
Technical Field
The invention relates to Fe doped Mn with a hollow nano-framework structure3O4A preparation method of a carbon and nitrogen material, the material obtained by the preparation method and the electrocatalysis application of oxygen reduction reaction, belonging to the technical field of zinc-air battery anode catalysts.
Background
The electrochemical rechargeable zinc-air battery has the characteristics of high energy density, safe water system electrolyte, strong economy and the like, has wide application prospect in the aspects of electric automobiles, portable power supplies and large-scale energy storage, and is an important industrial direction for developing green and clean energy. As a potential electrochemical energy storage device, zinc-air batteries are widely concerned by researchers due to the characteristics of low cost, abundant resources, environmental friendliness, high energy density and the like. The Oxygen Reduction Reaction (ORR) plays an important role in a series of energy conversion devices such as metal air batteries and fuel cells. However, the reaction process involves a multi-step proton-coupled electron transfer process, which is kinetically slow, and therefore, it is necessary to select a suitable catalyst to improve the reaction rate and efficiency. Noble metal Pt and its alloys are the best ORR catalysts at present, but the reserves are rare, the price is expensive, and the catalyst is not suitable for large-scale application. Therefore, it is particularly important to develop a novel catalyst with low cost, high efficiency and stability to replace the noble metal Pt-based catalyst.
In recent years, hollow micro/nano structures have a wide application prospect due to the unique structure-induced physicochemical properties, and particularly attract attention in the aspects of electrochemical energy storage and conversion. Among them, Prussian Blue (PB) and its analogues (PBA) have been studied in large quantities due to their low cost, high performance, open structure, adjustable composition, etc. (Advanced Materials, 2017,201706825; Advanced Materials,2018,30, 201800939). The results of the studies show that cation exchange is an effective method for preparing hollow inorganic nanoparticles, MA(MAFe, Mn, Ni, Cu, Zn, V, Mo, Ce, Gd, etc. -MB(MBFe, Co, etc.) PBA can be easily formed from the metal oxide MAMBOx(MAFe, Mn, Ni, Cu, Zn, V, Mo, Ce, Gd, etc.; mBFe, Co, etc.) to produce a hollow nano-framework structure. Hollow structures are considered to be superior to solid structures in terms of electrocatalysis, because hollow structures can provide moreHigh catalytic interface area, thereby remarkably improving the electrocatalytic performance. In order to make PBA practically applied in electrochemical energy storage, ionic conductivity and electronic conductivity must be greatly improved, and mixing or coating conductive carbon materials (such as graphene and carbon nanotubes) is an effective method for improving electronic conductivity, and the nanocarbon materials not only can effectively improve the conductivity of the catalyst, but also provide a larger specific surface area and improve the stability of active species. Meanwhile, the doping of hetero atoms (such as N, P, S and the like) into the carbon matrix can effectively improve the catalytic performance by adjusting the electronic structure of the nearby carbon atoms. Therefore, the synergistic advantages are combined to synthesize Fe doped Mn with hollow nano framework structure3O4Carbon nitrogen material is a sensible strategy. However, in general, the preparation of such materials tends to be time-consuming, tedious, and low-yielding.
Disclosure of Invention
To solve the above technical problems, the present invention provides a Fe-doped Mn with a hollow nano-framework structure3O4A preparation method and application of a carbon and nitrogen material. The method is simple and universal, the cost is low, and the prepared Prussian blue analogue derivative Fe is doped with Mn3O4The carbon-nitrogen material is used as an oxygen reduction electrocatalyst, shows excellent activity and stability, and can be used as a high-efficiency zinc-air battery anode electrocatalyst material.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1) preparation of Fe (CN)6 3-PVP solution and Mn2+A solution;
2) mixing said Fe (CN)6 3-PVP solution and Mn2+The solution was mixed well and allowed to stand to give KMnFe (CN)6Precipitating;
3) mixing the KMnFe (CN)6Alkali washing the precipitate with sodium hydroxide solution, heating to 2 deg.C in inert atmospherePerforming heat treatment at 50-350 ℃ to obtain the Fe-doped Mn with the hollow nano-frame structure3O4A carbon nitrogen material.
Preferably, K is3Fe(CN)6The preparation method of the/PVP solution comprises the following steps:
dissolving PVP and potassium ferricyanide in water, and uniformly mixing to obtain the K3Fe(CN)6PVP solution.
Preferably, K is3Fe(CN)6In the PVP solution, the mass fraction of PVP is 5-10%.
Preferably, the Mn is contained2+The preparation method of the solution comprises the following steps:
dissolving manganese chloride in water.
Preferably, K is3Fe(CN)6PVP solution and Mn-containing solution2+After mixing the solution of (1), Mn2+And Fe3+The molar ratio of (A) to (B) is 2:1 to 1: 2.
Preferably, the concentration of the sodium hydroxide solution used for the alkaline washing is 0.2M, and the temperature of the alkaline washing is 40 ℃.
Preferably, the heating rate is 1-10 ℃/min, and the heat treatment time is 2-4 h.
Preferably, the inert atmosphere is at least one of nitrogen, argon, helium and carbon dioxide.
Fe doped Mn derived from Prussian blue analogue prepared by the preparation method3O4The carbon-nitrogen material can be used as an anode electrocatalyst of a zinc-air battery, and has remarkable effect.
The reaction principle of the invention is as follows: preparing KMnFe (CN) in advance by cyano coordination with potassium ferricyanide and manganese chloride as metal sources and polyvinylpyrrolidone as a carbon source and a weak reducing agent6Prussian blue analogue, reaction induction using NaOH solution and reaction in N2Preparing Fe doped Mn derived from hollow nano-framework structure Prussian blue analogue by high-temperature carbonization in atmosphere3O4The carbon nitrogen material of (1). The material has regular and uniform appearance. In addition, the material containsHas rich N element and Mn doped with active Fe due to the hollow nanometer frame structure3O4The obtained material has higher oxygen reduction activity and excellent stability.
The Prussian blue analogue-derived Fe doped Mn with the hollow nano-framework structure prepared by the invention3O4The carbon and nitrogen material has the following advantages:
1) the hollow nano-framework structure has larger specific surface area, exposes more active sites, and can effectively promote the contact of electrolyte and a catalyst, thereby being beneficial to the generation of reaction;
2) the permeable shell layer with the thinner hollow nano framework structure can effectively shorten the diffusion path of ions and electrons, directionally promote the rapid transmission of the electrons and the ions, improve the catalytic reaction rate, and promote the reaction of reactants and the rapid output of products;
3) the hollow nano-frame structure has a larger internal buffer area, so that the hollow nano-frame structure is not easy to agglomerate in the reaction process, and O is effectively relieved2Molecule and OH-The structural strain caused by the ion adsorption and diffusion processes is adapted to possible volume change, and the structural integrity is maintained;
4) PVP with higher nitrogen content is selected as a carbon source and a reducing agent, and Fe (CN) is controlled in a solution phase6 3-With Mn2+So that it slowly and uniformly generates KMnFe (CN)6The carbon carrier with higher graphitization degree and better thermal stability can be generated by high-temperature carbonization and reduction, and the conductivity of the carbon carrier can be effectively changed by doping nitrogen, so that the oxygen reduction performance of the material is improved.
The technical effects are as follows: compared with the prior art, the invention has the following advantages:
1) the Prussian blue analogue derived Fe doped Mn with a hollow nano-framework structure is prepared by combining a simple Prussian blue analogue preparation method capable of realizing large-scale production and high-temperature carbonization thermal reduction3O4The carbon-nitrogen electrocatalyst material of (1);
2) the PVP and the transition metals Fe and Mn are cheap and easy to obtain, and compared with the traditional method for preparing the zinc-air electrocatalyst material, the method has the advantages of simple and feasible process, low cost, simple operation and capability of realizing large-scale production;
3) the prepared product has regular shape, the unique hollow nano-framework structure can expose more active sites, the transmission of ions and electrons and the reaction of electrolyte and catalyst are effectively promoted, compared with the conventional solid structure material, the prepared electro-catalyst material derived from the hollow nano-framework structure Prussian blue analogue has more excellent structural characteristics and component advantages, is a zinc-air battery anode electro-catalyst material with great potential, and is expected to have wide application prospect in the future energy industry.
Drawings
FIG. 1 shows Fe-doped Mn with hollow nano-framework structure prepared according to example 1 of the present invention3O4Low power SEM spectra of carbon and nitrogen materials;
FIG. 2 shows Fe-doped Mn with hollow nano-framework structure prepared according to example 1 of the present invention3O4TEM spectra of the carbon and nitrogen material;
FIG. 3 shows Fe-doped Mn with hollow nano-framework structure prepared according to example 1 of the present invention3O4XRD patterns of carbon and nitrogen materials;
FIG. 4 shows Fe doped Mn with hollow nano-framework structure prepared in example 1 of the present invention3O4LSV curves of carbon and nitrogen materials versus other comparative materials;
FIG. 5 shows Fe-doped Mn with hollow nano-framework structure prepared according to example 1 of the present invention3O4Comparing LSV curves of the carbon and nitrogen materials in a test environment with or without methanol poisoning;
FIG. 6 shows Fe-doped Mn with hollow nano-framework structure prepared according to example 1 of the present invention3O4Tafel curve of carbon and nitrogen material;
FIG. 7 shows Fe-doped Mn with hollow nano-framework structure prepared according to example 1 of the present invention3O4Timing device for carbon and nitrogen materialA flow test curve;
FIG. 8 is a comparison of discharge polarization curves for example 1 and a commercial Pt/C material according to the present invention;
FIG. 9 shows Fe-doped Mn with hollow nano-framework structure prepared according to example 1 of the present invention3O4TEM atlas after carbon nitrogen material circulation stability test.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
The Fe with the hollow nano-framework structure prepared in the above embodiment is doped with Mn by adopting SEM, TEM, XRD and other approaches3O4The carbon nitrogen material was physically characterized. From the SEM (fig. 1), it can be seen that prussian blue analogue derived Fe doped Mn3O4Hollow cube block with uniformly distributed carbon and nitrogen materialsThe structure is characterized in that more nano sheets are grown around the structure, and a further enlarged TEM image (figure 2) can show that the prepared material has the structure, and the side length of a cubic block is about 600 nm. As can be seen from the XRD spectrum in figure 3, the diffraction peak of the material can be associated with Mn3O4The standard cards of (JCPDS No.18-0804) proved that Fe was successfully doped into Mn3O4While the (002) crystal face corresponds to the diffraction peak of the graphitized carbon. FIG. 4 is a LSV curve diagram obtained by testing the oxygen reduction performance of the catalyst and other samples under the test environment, and it can be seen that the prepared Fe-doped Mn3O4The carbon and nitrogen material has excellent initial reduction potential and half-wave potential. Fig. 5 is a LSV curve obtained by performing an oxygen reduction performance test on the material in a test environment with or without methanol poisoning, and it can be seen from the LSV curves of the two tests are still almost overlapped in the test environment with methanol poisoning, which indicates that the catalyst material has good alcohol resistance. The Tafel curve (FIG. 6) shows that the Tafel slope of the material has a value of only 82.3mV dec-1This is superior to most oxygen-reducing electrocatalyst materials, indicating that the materials have faster reaction kinetic rates. Fig. 7 is a chronoamperometric curve of the material, and the sample has smaller current density attenuation after being tested for a long time of 40000s, which also shows that the material has excellent cycle stability. Fig. 8 is a charge-discharge polarization curve diagram of the material and a commercial Pt/C catalyst after being assembled into a zinc-air battery, and it can be seen that the material has higher power density under high current density. The TEM pattern (figure 9) after the cycle stability test shows that the hollow nano framework structure of the material still exists and the volume has no obvious change, and the phenomenon shows that the hollow structure has effective buffering effect. The results show that the material has good application prospect as the zinc-air battery anode catalyst material.
Example 2
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.5g of PVP and 1.0mmol of PVP were weighed outK of3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 3
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 4.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Under the atmosphere, the temperature rises at the rate of 5 ℃/minAnd (3) heating to 300 ℃, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 4
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 0.83mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.67mmol of MnCl was weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 5
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.25mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.25mmol of MnCl is weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 6
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.67mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 0.83mmol of MnCl is weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 7
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6root of rehmanniaPreparation of color precipitate: 3.0g PVP and 0.5mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 0.75mmol of MnCl is weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 8
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed with alkali in 2.0M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 9
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 30 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 10
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (b), (c), (d), (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 50 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 300 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 11
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed by alkali in 0.2M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 250 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3 hours, and then cooling to room temperature to obtain the final product.
Example 12
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed with alkali in 2.0M NaOH solution at 40 ℃ for 4h to obtain a solid powdery material which is firstly centrifugally washed and dried and then is put in N2Heating to 350 ℃ at the heating rate of 5 ℃/min under the atmosphere for heat treatment, keeping the temperature for 3h, and then cooling to room temperature to obtain the final product.
Example 13
Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material comprises the following steps:
1)KMnFe(CN)6preparation of a khaki precipitate: 3.0g PVP and 1.0mmol K were weighed3Fe(CN)6·3H2O solid Metal salt with 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Fe (CN)6 3-A PVP solution; 1.5mmol of MnCl are weighed2With 50ml H2Mixing the O solution, and mechanically stirring at room temperature for 10min to obtain Mn2+A solution; mixing Fe (CN)6 3-PVP solution and Mn2+The solutions were mixed and allowed to stand for 12h to yield KMnFe (CN)6Yellow precipitate;
2) preparation of Fe-doped Mn with hollow nano-framework structure3O4Carbon and nitrogen material: KMnFe (CN) prepared in the step 1)6The earthy yellow precipitate is washed with alkali in 0.2M NaOH solution for 4h at 40 ℃ to obtain solid powdery material,firstly, centrifugally washing and drying, then heating to 300 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere for heat treatment, keeping the temperature for 3h, and then cooling to room temperature to obtain the final product.
Example 14
The same as example 1, except that:
resulting Fe (CN)6 3-In the PVP solution, the mass fraction of PVP is 5 percent; the temperature programming rate is 1 ℃/min, the heat treatment temperature is 200 ℃, and the time is 2 h.
Example 15
The same as example 1, except that:
resulting Fe (CN)6 3-In the PVP solution, the mass fraction of PVP is 10 percent; the temperature programming rate is 10 ℃/min, the heat treatment temperature is 300 ℃, and the time is 4 h.
Comparative example 1
This comparative example differs from example 1 only in that no alkaline washing with 0.2M NaOH solution was carried out, the remaining operating conditions being unchanged.
Comparative example 2
This comparative example differs from example 1 only in that ferric chloride was used instead of the manganese chloride metal source and the remaining operating conditions were unchanged.
The LSV test results of the oxygen reduction reaction of the corresponding test are shown in fig. 4, and the material obtained without NaOH alkaline washing shows the most negative initial reduction potential and the least current density, showing the worst oxygen reduction performance; fe obtained by replacing metal source3O4The carbon-nitrogen electro-catalytic material shows Mn doping compared with Fe3O4Carbon and nitrogen materials have poor oxygen reduction properties. The overall comparison of properties shows Fe-Mn3O4>Fe3O4>Fe-Mn3O4(without NaOH caustic wash). Fe doped Mn of prepared hollow nano-framework structure3O4The carbon-nitrogen material electrocatalysis shows oxygen reduction performance which is comparable to commercial Pt/C, and has higher specific capacity and more excellent cycle stability when being applied to a zinc-air battery.

Claims (10)

1. Fe-doped Mn with hollow nano-framework structure3O4The preparation method of the carbon and nitrogen material is characterized by comprising the following steps:
1) preparation of K separately3Fe(CN)6PVP solution and Mn-containing solution2+The solution of (1);
2) the K is added3Fe(CN)6PVP solution and Mn-containing solution2+Is mixed to obtain KMnFe (CN)6Precipitating;
3) mixing the KMnFe (CN)6Alkali washing the precipitate with sodium hydroxide solution, heating to 250-350 ℃ in inert atmosphere, and performing heat treatment to obtain the Fe-doped Mn with the hollow nano-framework structure3O4A carbon nitrogen material.
2. Fe-doped Mn with hollow nano-framework structure according to claim 13O4A method for producing a carbon-nitrogen material, characterized in that K is3Fe(CN)6The preparation method of the/PVP solution comprises the following steps:
dissolving PVP and potassium ferricyanide in water, and uniformly mixing to obtain the K3Fe(CN)6PVP solution.
3. Fe-doped Mn with hollow nano-framework structure according to claim 23O4A method for producing a carbon-nitrogen material, characterized in that K is3Fe(CN)6In the PVP solution, the mass fraction of PVP is 5-10%.
4. Fe-doped Mn with hollow nano-framework structure according to claim 13O4Method for producing a carbon-nitrogen material, characterized in that the Mn-containing material2+The preparation method of the solution comprises the following steps:
dissolving manganese chloride in water.
5. Fe-doped Mn with hollow nano-framework structure according to claim 13O4A method for producing a carbon-nitrogen material, characterized in that K is3Fe(CN)6PVP solution and Mn-containing solution2+After mixing the solution of (1), Mn2+And Fe3+The molar ratio of (A) to (B) is 2:1 to 1: 2.
6. Fe-doped Mn with hollow nano-framework structure according to claim 13O4The preparation method of the carbon and nitrogen material is characterized in that the concentration of a sodium hydroxide solution used for alkaline washing is 0.2M, and the temperature of the alkaline washing is 40 ℃.
7. Fe-doped Mn with hollow nano-framework structure according to claim 13O4The preparation method of the carbon and nitrogen material is characterized in that the heating rate is 1-10 ℃/min, and the heat treatment time is 2-4 h.
8. Fe-doped Mn with hollow nano-framework structure according to claim 13O4The preparation method of the carbon and nitrogen material is characterized in that the inert atmosphere is at least one of nitrogen, argon, helium and carbon dioxide.
9. Fe-doped Mn with hollow nano-framework structure obtained by the preparation method of claim 13O4A carbon nitrogen material.
10. Fe-doped Mn with hollow nano-framework structure of claim 93O4Use of a carbon-nitrogen material as a positive electrode material for a zinc-air battery.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106960954A (en) * 2017-05-17 2017-07-18 哈尔滨工业大学 A kind of preparation method and application of Prussian blue/graphene/sulphur composite
CN107123553A (en) * 2017-01-10 2017-09-01 新疆大学 One kind prepares Mn using MOF templates3O4The method of hollow micro-nano cubic block
CN107317002A (en) * 2017-06-16 2017-11-03 电子科技大学 A kind of prussian blue comprehensive silicon negative material and preparation method thereof
CN107335431A (en) * 2017-06-26 2017-11-10 南京师范大学 A kind of preparation method of embedded porous Pd/C nanometers framework and its resulting materials and application
CN108133832A (en) * 2017-12-05 2018-06-08 西北工业大学 A kind of nano hollow structure is Prussian blue and its preparation method of homologue
CN108878803A (en) * 2018-05-23 2018-11-23 广东工业大学 A kind of Prussian blue similar object electrode material of hollow core-shell structure and its preparation method and application
CN109248703A (en) * 2018-09-12 2019-01-22 南京师范大学 A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018064347A1 (en) * 2016-09-28 2018-04-05 California Institute Of Technology Tuning electrode surface electronics with thin layers

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107123553A (en) * 2017-01-10 2017-09-01 新疆大学 One kind prepares Mn using MOF templates3O4The method of hollow micro-nano cubic block
CN106960954A (en) * 2017-05-17 2017-07-18 哈尔滨工业大学 A kind of preparation method and application of Prussian blue/graphene/sulphur composite
CN107317002A (en) * 2017-06-16 2017-11-03 电子科技大学 A kind of prussian blue comprehensive silicon negative material and preparation method thereof
CN107335431A (en) * 2017-06-26 2017-11-10 南京师范大学 A kind of preparation method of embedded porous Pd/C nanometers framework and its resulting materials and application
CN108133832A (en) * 2017-12-05 2018-06-08 西北工业大学 A kind of nano hollow structure is Prussian blue and its preparation method of homologue
CN108878803A (en) * 2018-05-23 2018-11-23 广东工业大学 A kind of Prussian blue similar object electrode material of hollow core-shell structure and its preparation method and application
CN109248703A (en) * 2018-09-12 2019-01-22 南京师范大学 A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Highly Porous Mn3 O4 Micro/Nanocuboids with In Situ Coated Carbon as Advanced Anode Material for Lithium-Ion Batteries;Jiang Yao, Yue Ji-Li, Guo Qiubo, et al.;《Small》;20181231;正文 *
Spin-glass behavior of the polyvinyl pyrrolidone-protected Prussian blue analog K 1.14 Mn[Fe(CN) 6 ] 0.88 nanocubes;Bo Gao,Jinli Yao,Desheng Xue;《Physica B：Condensed Matter》;20110615;正文 *

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