CN113097499A - FeNi/NiFe2O4@ NC composite material and preparation method and application thereof - Google Patents

FeNi/NiFe2O4@ NC composite material and preparation method and application thereof Download PDF

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CN113097499A
CN113097499A CN202110338598.5A CN202110338598A CN113097499A CN 113097499 A CN113097499 A CN 113097499A CN 202110338598 A CN202110338598 A CN 202110338598A CN 113097499 A CN113097499 A CN 113097499A
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feni
nife
composite material
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CN113097499B (en
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卞婷
王浩权
苏珊
于涛
何泽杨
黄龙
左林致
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Jiangsu University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses FeNi/NiFe2O4@ NC composite material of FeNi/NiFe2O4The @ NC is porous sponge-shaped and comprises the following elements in percentage by mass: c: 70-73 wt%, N: 3-4 wt%, Fe: 10-12 wt%, Ni: 12-13 wt%, and the balance of O. The invention discloses FeNi/NiFe2O4A preparation method of the @ NC composite material. The invention discloses FeNi/NiFe2O4The application of the @ NC composite material as an electrocatalyst in the cathode oxygen reduction reaction of a fuel cell. The composite material has good stability, the FeNi alloy and the nitrogen-doped carbon layer have synergistic effect, and the composite material has good oxygen reduction reactionElectrocatalytic properties; the preparation method is simple and convenient, easy to control, uniform in appearance and size and good in dispersity, and the FeNi bimetallic metal organic framework with good appearance can be successfully obtained.

Description

FeNi/NiFe2O4@ NC composite material and preparation method and application thereof
Technical Field
The invention relates to a composite material, a preparation method and application thereof, in particular to FeNi/NiFe2O4A @ NC composite material and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of low operating temperature, high power density, and fast reaction speed, and are widely developed in the fields of distributed power generation, portable electronic applications, and automobiles. However, since the fuel cell cathode Oxygen Reduction Reaction (ORR) is accompanied by a complicated four-electron transfer process, the intrinsic kinetic rate is slow, and thus the efficiency of the oxygen reduction reaction becomes a key factor limiting the performance of the fuel cell.
Although platinum (Pt) and Pt-based alloys are highly efficient for ORR, their high cost and scarce reserves in nature have largely hindered their large-scale practical application. Therefore, it is crucial to develop low-cost non-noble metal-based catalysts as alternatives to Pt-based catalysts.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide FeNi/NiFe with good stability and good catalytic effect2O4The invention also aims to provide a FeNi/NiFe composite material which is low in cost, simple and convenient2O4The invention also aims to provide a preparation method of the @ NC composite material2O4The application of the @ NC composite material as an electrocatalyst in the cathode oxygen reduction reaction of a fuel cell.
The technical scheme is as follows: the invention relates to FeNi/NiFe2O4@ NC composite material, composite material FeNi/NiFe2O4@ NC is porous sponge-like and contains the following elements in percentage by mass: c: 70-73 wt%, N: 3-4 wt%, Fe: 10-12 wt%, Ni: 12-13 wt%, and the balance of O.
Further, FeNi and NiFe2O4And the nano-crystalline particles which are jointly formed are loaded in the cube of the porous NC. In order to obtain a Hofmann type metal organic framework nanocube with a good appearance, the molar ratio of Fe element, Ni element, organic ligand and surfactant is 1:1:1: 20.
The above FeNi/NiFe2O4The preparation method of the @ NC composite material comprises the following steps:
step one, respectively dissolving an organic ligand, a surfactant and an iron precursor in a mixed solution of methanol and water, K2[Ni(CN)4]Dissolving the mixture in water, and stirring for reaction to obtain a Hofmann FeNi bimetallic metal organic framework with uniform appearance and size;
step two, heating the nanocubes obtained in the step one to 700-900 ℃ at the speed of 5 ℃/min under the protection of inert gas, and performing high-temperature pyrolysis to obtain porous spongy FeNi/NiFe2O4@ NC composite material.
Furthermore, the organic ligand is 4, 4-bipyridine, 4-azopyridine or pyrazine, has a good plane structure and an axial position, and is favorable for forming a regular pore channel structure. The concentration of the organic ligand is 0.005-0.01 mol/L. The concentration is lower than 0.005mol/L, a FeNi bimetallic metal organic framework of a Hofmann type cannot be effectively formed, the yield is low, the concentration is higher than 0.01mol/L, and the size of a product is greatly reduced due to overhigh concentration of a ligand under the condition of fixing the concentration of other precursors to be unchanged, so that the subsequent centrifugal collection is difficult.
Furthermore, the surfactant is polyvinylpyrrolidone or polyethylene glycol, is used for regulating and controlling the morphology structure of the obtained product, and can also be used as a reducing agent to prevent ferrous salt from being oxidized. The concentration of the surfactant is 0.1-0.2 mol/L. The concentration is lower than 0.1mol/L, the product appearance is irregular, the size is different, the concentration is higher than 0.2mol/L, the products are mutually bonded, and the dispersibility is poor.
Further, the iron precursor is any one of ferric tetrafluoroborate, ferrous sulfate, ferrous chloride and ferrous bromide. The concentration of the iron precursor is 0.005-0.01 mol/L. The concentration of the iron precursor is lower than 0.005mol/L, which leads to lower yield of the final product, and the concentration is higher than 0.01mol/L, which leads to uneven appearance and agglomeration among products.
The above FeNi/NiFe2O4The application of the @ NC composite material as an electrocatalyst in the cathode oxygen reduction reaction of a fuel cell.
The working principle is as follows: the metal raw material is inorganic salt, and the ligand is organic matter, so the mixed solution of methanol and water is selected as the solvent. In order to obtain the Hofmann type bi-component FeNi metal organic framework nanocube, a Ni metal precursor needs to be tetracyanonickelate, and a Fe metal precursor is ferrite. Porous spongy FeNi/NiFe2O4The @ NC composite material is favorable for electron transmission and oxygen diffusion, and the porous structure has a larger active area and can expose more active sites. Meanwhile, the stability of the composite material is improved by the synergistic effect of the FeNi alloy and the nitrogen-doped carbon layer, and more favorable conditions are provided for catalytic reaction.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1、FeNi/NiFe2O4the @ NC composite material has good stability and good electrocatalytic performance of oxygen reduction reaction, the FeNi alloy and the nitrogen-doped carbon layer have a synergistic effect, the catalytic efficiency is high, and the porous structure is favorable for oxygen diffusion and exposing more active sites;
2. the preparation method is simple and convenient, easy to control, uniform in appearance and size, good in dispersity, and capable of introducing Ni metal precursor K2[Ni(CN)4]The FeNi bimetallic metal organic framework with good appearance and a good Hofmann type can be successfully obtained; the metal atoms in the Hofmann metal organic framework and cyano groups (-CN) form a stable coordination structure and a regular pore channel structure, and under the influence of the coordination and the pore channel structure, atom aggregation can be effectively reduced in the pyrolysis process, and the atom utilization rate is improved;
3. the surfactant can regulate the shape and structure of the obtained product and can also be used as a reducing agent to prevent ferrous salt from being oxidized.
Drawings
FIG. 1 is a schematic representation of the spongy FeNi/NiFe obtained in example 12O4Scanning electron microscope images of @ NC composite materials;
FIG. 2 is the spongy FeNi/NiFe obtained in example 12O4Transmission electron micrograph of @ NC composite;
FIG. 3 is the spongy FeNi/NiFe obtained in example 12O4Transmission energy spectrogram of @ NC composite material;
FIG. 4 is the spongy FeNi/NiFe obtained in example 12O4Graph of oxygen reduction performance for @ NC composite with commercial Pt/C catalyst.
Detailed Description
The raw materials and the apparatus used in the following examples were purchased directly.
Example 1
Spongy FeNi/NiFe2O4The preparation method of the @ NC composite material comprises the following steps:
(1) at 25 ℃, 0.3mmol of ferric tetrafluoroborate Fe (BF) is added4)2Dissolving the mixture in 40mL of mixed solution of methanol and water in a volume ratio of 1:1 to obtain mixed solution with the ferric salt concentration of 0.0075mol/L as solution A;
(2) dissolving 6mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.3mmol of organic ligand 4, 4-bipyridine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with ligand concentration of 0.0075mol/L as solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel salt concentration of 0.03mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reaction for 3 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 800 ℃ in a tubular furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 71.35 wt%, N: 3.2 wt%, Fe: 10.5 wt%, Ni: 12.12 wt%, O: 2.83 wt%.
FIG. 1 shows the spongy FeNi/NiFe obtained in example 12O4The scanning electron microscope image of the @ NC composite material has the magnification of 10000, and the composite material is shown to be in a nanocube structure.
FIG. 2 shows the spongy FeNi/NiFe obtained in example 12O4Transmission electron micrograph of @ NC composite material, its magnification is 150000. As can be seen from the transmission electron micrograph of FIG. 2, the spongy FeNi/NiFe prepared in example 12O4The @ NC composite material takes nitrogen-doped carbon material as a substrate, and FeNi alloy and NiFe are loaded on the substrate2O4The metal nanocrystalline formed by the metal oxides is of a porous spongy structure as a whole.
FIG. 3 shows the spongy FeNi/NiFe obtained in example 12O4The transmission energy spectrogram of the @ NC composite material can be seen to contain C elements, N elements, Fe elements and Ni elements, and the magnification of FIG. 3 is 180000.
For the spongy FeNi/NiFe obtained in example 12O4Electrochemical performance test is carried out on the @ NC composite material, FIG. 4 is a corresponding oxygen reduction performance curve diagram, and as can be seen from FIG. 4, the spongy FeNi/NiFe prepared in example 12O4The onset potentials of the @ NC composite material and the commercial Pt/C catalyst were 1V (vs. RHE) and 0.98V (vs. RHE), respectively, and the half-wave potentials were 0.86V (vs. RHE) and 0.83V (vs. RHE), respectively, whereby it was found that the spongy FeNi/NiFe obtained in example 12O4The oxygen reduction catalytic performance of the @ NC composite material is superior to that of the commercial Pt/C catalystReagent, thus illustrating the spongy FeNi/NiFe of the present invention2O4The @ NC composite material has excellent oxygen reduction catalytic performance.
Example 2
(1) At 25 ℃, 0.2mmol of ferric tetrafluoroborate Fe (BF) is added4)2Dissolving the mixed solution in 40mL of methanol and water at a volume ratio of 1:1 to obtain a mixed solution with the concentration of iron salt of 0.005mol/L as a solution A;
(2) dissolving 4mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.2mmol of organic ligand 4, 4-bipyridine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with ligand concentration of 0.005mol/L as solution B;
(3) adding 0.2mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel salt concentration of 0.02mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 2 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 750 ℃ in a tube furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 70.06 wt%, N: 3.89 wt%, Fe: 10.46 wt%, Ni: 12.28 wt%, O: 3.31 wt%.
Example 3
(1) At 25 ℃, 0.4mmol of ferric tetrafluoroborate Fe (BF) is added4)2Dissolving the mixed solution in 40mL of methanol and water at a volume ratio of 1:1 to obtain a mixed solution with the ferric salt concentration of 0.01mol/L as a solution A;
(2) dissolving 8mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.4mmol of organic ligand 4, 4-bipyridine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with ligand concentration of 0.01mol/L as solution B;
(3) adding 0.4mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel salt concentration of 0.04mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reaction for 3 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 900 ℃ in a tubular furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 72.85 wt%, N: 3.21 wt%, Fe: 10.3 wt%, Ni: 12.52 wt%, O: 1.12 wt%.
Example 4
(1) At 10 deg.C, 0.3mmol of ferric tetrafluoroborate Fe (BF)4)2Dissolving the mixture in 40mL of mixed solution of methanol and water in a volume ratio of 1:1 to obtain mixed solution with the ferric salt concentration of 0.0075mol/L as solution A;
(2) dissolving 6mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.3mmol of organic ligand 4, 4-bipyridine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with ligand concentration of 0.0075mol/L as solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolved in 10mL of water to obtain an aqueous solution having a nickel salt concentration of 0.03mol/L as a solutionLiquid C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 4 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 850 ℃ in a tubular furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 71.62 wt%, N: 3.16 wt%, Fe: 11.33 wt%, Ni: 12.05 wt%, O: 1.84 wt%.
Example 5
(1) At 60 ℃, 0.4mmol of ferric tetrafluoroborate Fe (BF) is added4)2Dissolving the mixed solution in 40mL of methanol and water at a volume ratio of 1:1 to obtain a mixed solution with the ferric salt concentration of 0.01mol/L as a solution A;
(2) dissolving 8mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.4mmol of organic ligand 4, 4-bipyridine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with ligand concentration of 0.01mol/L as solution B;
(3) adding 0.4mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel salt concentration of 0.04mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 2 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 800 ℃ in a tubular furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 71.65 wt%, N: 3.41 wt%, Fe: 10.18 wt%, Ni: 12.29 wt%, O: 2.47 wt%.
Example 6
(1) At 60 ℃, 0.2mmol of ferrous bromide (FeBr)2) Dissolving the mixed solution in 40mL of methanol and water at a volume ratio of 1:1 to obtain a mixed solution with the concentration of iron salt of 0.005mol/L as a solution A;
(2) dissolving 8mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.2mmol of organic ligand 4, 4-bipyridine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with ligand concentration of 0.005mol/L as solution B;
(3) adding 0.2mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel salt concentration of 0.02mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 4 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 900 ℃ in a tubular furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 70.15 wt%, N: 3.57 wt%, Fe: 11.52 wt%, Ni: 12.38 percent by weight of the total weight of the steel,O：2.38wt％。
example 7
(1) At 25 ℃, 0.3mmol of ferrous chloride (FeCl)2) Dissolving the mixture in 40mL of mixed solution of methanol and water in a volume ratio of 1:1 to obtain mixed solution with the ferric salt concentration of 0.0075mol/L as solution A;
(2) dissolving 6mmol of surfactant K-29 type polyvinylpyrrolidone (PVP) and 0.3mmol of organic ligand 4, 4-azopyridine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain mixed solution with ligand concentration of 0.0075mol/L as solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel salt concentration of 0.03mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reacting for 2 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 900 ℃ in a tubular furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 70.93 wt%, N: 3.96 wt%, Fe: 11.72 wt%, Ni: 12.17 wt%, O: 1.22 wt%.
Example 8
(1) At 10 ℃, 0.3mmol of ferrous sulfate (FeSO)4) Dissolving the mixture in 40mL of mixed solution of methanol and water in a volume ratio of 1:1 to obtain mixed solution with the ferric salt concentration of 0.0075mol/L as solution A;
(2) dissolving 6mmol of surfactant polyethylene glycol (PEG-2000) and 0.3mmol of organic ligand pyrazine in 40mL of mixed solution of methanol and water in a volume ratio of 1:1, and performing ultrasonic treatment for 1-2 min to obtain a mixed solution with a ligand concentration of 0.0075mol/L as a solution B;
(3) adding 0.3mmol K of potassium tetracyanonickelate2[Ni(CN)4]Dissolving in 10mL of water to obtain an aqueous solution with the nickel salt concentration of 0.03mol/L as a solution C;
(4) slowly dripping the solution B into the solution A under magnetic stirring to obtain a light yellow solution;
(5) slowly dripping the solution C into the mixed solution obtained in the step (4), and continuously stirring for reaction for 3 hours to obtain an orange solution;
(6) centrifuging and washing the product obtained in the step (5) for three times by water, removing supernatant, taking precipitate, and drying at 50 ℃ overnight to obtain orange powder;
(7) putting a proper amount of the powder obtained in the step (6) into a porcelain boat, heating the porcelain boat to 900 ℃ in a tubular furnace at the heating rate of 5 ℃/min, reacting for 2h, and naturally cooling to normal temperature to obtain FeNi/NiFe2O4@ NC composite material.
For the obtained FeNi/NiFe2O4The @ NC composite material is subjected to EDS analysis, and the composition of each element is as follows: c: 72.92 wt%, N: 3.13 wt%, Fe: 10.88 wt%, Ni: 11.92 wt%, O: 1.15 wt%.

Claims (10)

1. FeNi/NiFe2O4The @ NC composite material is characterized in that: the composite material is FeNi/NiFe2O4The @ NC is porous sponge-shaped and comprises the following elements in percentage by mass: c: 70-73 wt%, N: 3-4 wt%, Fe: 10-12 wt%, Ni: 12-13 wt%, and the balance of O.
2. FeNi/NiFe as claimed in claim 12O4The @ NC composite material is characterized in that: the FeNi and the NiFe2O4And the nano-crystalline particles which are jointly formed are loaded in the cube of the porous NC.
3. FeNi/NiFe as claimed in any one of claims 1 to 22O4Method for the production of @ NC composites, and the sameIs characterized by comprising the following steps:
step one, respectively dissolving an organic ligand, a surfactant and an iron precursor in a mixed solution of methanol and water, K2[Ni(CN)4]Dissolving the mixture in water, and stirring for reaction to obtain a Hofmann FeNi bimetallic metal organic framework;
step two, pyrolyzing the nanocubes obtained in the step one at high temperature of 700-900 ℃ under the protection of inert gas to obtain porous spongy FeNi/NiFe2O4@ NC composite material.
4. FeNi/NiFe as claimed in claim 32O4The @ NC composite material is characterized in that: the organic ligand is 4, 4-bipyridine, 4-azopyridine or pyrazine.
5. A FeNi/NiFe as claimed in claim 3 or 42O4The @ NC composite material is characterized in that: the concentration of the organic ligand is 0.005-0.01 mol/L.
6. FeNi/NiFe as claimed in claim 32O4The @ NC composite material is characterized in that: the surfactant is polyvinylpyrrolidone or polyethylene glycol.
7. A FeNi/NiFe as claimed in claim 3 or 62O4The @ NC composite material is characterized in that: the concentration of the surfactant is 0.1-0.2 mol/L.
8. FeNi/NiFe as claimed in claim 32O4The @ NC composite material is characterized in that: the iron precursor is any one of ferric tetrafluoroborate, ferrous sulfate, ferrous chloride and ferrous bromide.
9. FeNi/NiFe as claimed in claim 82O4The @ NC composite material is characterized in that: the concentration of the iron precursor is 0.005-0.01 mol-L。
10. FeNi/NiFe as claimed in any one of claims 1 to 22O4The application of the @ NC composite material as an electrocatalyst in the cathode oxygen reduction reaction of a fuel cell.
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