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CN114433156B - Fe/Fe with 3D structure 3 C@FeNC difunctional oxygen electrocatalyst and preparation method and application thereof - Google Patents

Fe/Fe with 3D structure 3 C@FeNC difunctional oxygen electrocatalyst and preparation method and application thereof Download PDF

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CN114433156B
CN114433156B CN202210068403.4A CN202210068403A CN114433156B CN 114433156 B CN114433156 B CN 114433156B CN 202210068403 A CN202210068403 A CN 202210068403A CN 114433156 B CN114433156 B CN 114433156B
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fenc
pda
preparation
heating
microsphere
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CN114433156A (en
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黄乃宝
董文敬
孙先念
杨国刚
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Dalian Maritime University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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

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Abstract

The invention discloses a 3D structure Fe/Fe 3 A C@FeNC difunctional oxygen electrocatalyst and a preparation method and application thereof belong to the technical fields of energy materials and electrocatalysis. First, fe assembled from nanorods having a 3D structure was prepared 2 O 3 Microsphere, dopamine is formed into polydopamine coated on the room temperature alkaline condition through polycondensation reaction3D Fe 2 O 3 Fe of surface 2 O 3 @ PDA, then Fe in 3D structure 2 O 3 @PDA to a certain mass ratio g-C 3 N 4 Grinding uniformly, and finally, pyrolyzing at 600-700 ℃ to obtain Fe/Fe 3 C@FeNC difunctional oxygen electrocatalyst. The catalyst prepared by the invention can ensure the stability of a 3D structure while improving the nitrogen content, is beneficial to improving the ORR/OER catalytic property of the material, and has simple process and general usability.

Description

Fe/Fe with 3D structure 3 C@FeNC difunctional oxygen electrocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy materials and electrocatalysis, and in particular relates to a 3D structure Fe/Fe constructed by a dopamine protection strategy 3 C@FeNC difunctional oxygen electrocatalyst, and preparation method and application thereof.
Background
Oxygen Reduction Reactions (ORR) are widely used in both fuel cells and metal-air cells. The fuel cell, the metal air cell and other energy devices have the advantages of high energy conversion efficiency, environmental friendliness and the like, and have important significance for solving the increasingly severe problems of energy shortage and environmental pollution. However, the oxygen reduction reaction and the oxygen evolution reaction are complex in process, and involve a series of electrochemistry of multi-step electron transfer with slow kinetics, which are major problems for limiting the performance of the related energy devices. In order to solve the outstanding problem, a high-performance difunctional oxygen electrocatalyst is designed, so that the catalytic activity of the catalyst in ORR/OER is improved, the energy conversion efficiency can be greatly improved, and the method is important for developing an energy device.
At present, platinum (Pt) -based materials are widely considered as the best-performing ORR catalysts, and are the only commercially available ORR catalysts, irO 2 Is the OER catalyst with the best performance. But the shortage of noble metal resources such as Pt, ir and the like and higher cost severely limit the large-scale application of the noble metal. Thus, the preparation of Pt and Ir substituted catalysts with high activity and low cost is to realize fuel cells andthe key point of large-scale commercialization of metal-air batteries.
In recent years, attention has been paid to non-noble metal catalysts having high electrocatalytic activity, particularly iron-nitrogen co-doped carbon nanomaterials, since the Fe-N-C structure therein provides sufficient active sites for oxygen (O 2 ) And thus has excellent ORR catalytic activity. Many carbon nanocomposites with Fe-N-C structure have ORR performance settings comparable to commercial Pt-based catalysts. However, it contains Fe-N X The 3D structure of the ligand carbon material shows excellent ORR catalytic activity as an electrocatalyst, but the OER activity is not outstanding, which severely limits the application of the material in rechargeable zinc-air batteries.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method for constructing a difunctional oxygen electrocatalyst with a stable 3D structure and high nitrogen content by using a dopamine protection strategy. By Fe 2 O 3 Dopamine and g-C as templates and iron sources 3 N 4 Meanwhile, as a carbon source and a nitrogen source, firstly preparing Fe-glycerol microsphere with nano-plate assembly through hydrothermal reaction, and calcining in air to prepare Fe assembled by nano-rods 2 O 3 Microsphere, dopamine was then polymerized in Fe at room temperature 2 O 3 Surface is formed with Fe 2 O 3 @PDA，g-C 3 N 4 By milling with Fe as nitrogen-rich precursor 2 O 3 Uniformly mixing @ PDA, and carbonizing and coating the PDA in situ on Fe in the pyrolysis process 2 O 3 g-C 3 N 4 To CN gas, and the nitrogen atoms and the iron form Fe-N X A ligand. In addition, carbon acts as a reducing agent to reduce Fe 2 O 3 Reduced to iron simple substance, and part of the iron simple substance reacts with carbon to generate Fe 3 C. Wherein, the 3D hollow structure plays a great role in promoting the enhancement of the catalyst, and Fe-N X The ligand is the main active center of ORR, and the existence of the iron-based nano particles greatly enhances the OER activity of the catalyst. Fe/Fe synthesized by the method 3 C@FeNC catalyst with OER performance in 1M KOH solution of10mA cm -2 The corresponding voltage is 1.45V, which is superior to IrO 2 (1.51V) 60mV; the half-wave potential of ORR was 0.83V superior to the catalytic activity of commercial 20% Pt/C. Meanwhile, the prepared Fe/Fe 3 C@FeNC has better ORR and OER stability. The preparation process has universality.
The invention adopts the technical scheme that:
Fe/Fe with 3D structure 3 The preparation method of the C@FeNC difunctional oxygen electrocatalyst mainly comprises the following steps:
(1) Preparation of Fe 2 O 3 Microspheres: dispersing ferric salt into a solvent, transferring the mixed solution into a reaction vessel, reacting for 6-24 h at 160-220 ℃, washing, drying, heating to 350-450 ℃ in air atmosphere, and preserving heat for 2-5h to obtain Fe with 3D structure 2 O 3 A microsphere;
(2) Preparation of Fe 2 O 3 @ PDA: fe prepared in the step (1) 2 O 3 Dispersing the microspheres in deionized water, magnetically stirring for 0.5-5 h, adding tris (hydroxymethyl) aminomethane and dopamine, stirring and reacting for 2-10h under the condition of room temperature air to obtain Fe 2 O 3 PDA material;
(3) Preparation of g-C 3 N 4 : under the air atmosphere, melamine or urea is heated to 500-600 ℃, and the temperature is kept for 2-6 h to obtain g-C 3 N 4 ；
(4) Preparation of Fe/Fe 3 C@fenc microsphere catalyst: fe obtained in the step (2) 2 O 3 @ PDA with g-C 3 N 4 Grinding, mixing, heating to 600-700 deg.C in inert atmosphere, calcining for 0.5-3 hr to obtain Fe/Fe 3 C@FeNC difunctional oxygen electrocatalyst.
Further, the ferric salt in the step (1) comprises ferric nitrate, ferric sulfate and ferric chloride; the concentration of the ferric salt is 0.01-1 mM, and the solvent is a mixed solution of glycerol, isopropanol and deionized water.
Further, the volume ratio of glycerol, isopropanol and deionized water in the solvent is (5-10): (60-80): 1.
advancing oneStep (2), the reaction vessel in the step (1) is a high-pressure reaction kettle; the washing is to wash for 2-5 times by using alcohol and deionized water in turn, and the temperature rising rate is 1-3 ℃ for min -1 。
Further, fe in the step (2) 2 O 3 The mass ratio of the microsphere to the deionized water is (0.5-2): 1, fe 2 O 3 The mass ratio of the microsphere to the tris (hydroxymethyl) aminomethane to the dopamine is (2-6): 1: (2-4).
Further, the specific steps of the step (3) are that melamine or urea is added into a quartz boat, and is placed into a tube furnace, and the temperature is raised to 500-600 ℃ under the air atmosphere, and the temperature raising rate is 3-6 ℃ for min -1 Preserving heat for 2-6 h.
Further, the Fe in the step (4) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio of (2) is (50:1) to (1:2).
Further, the reaction furnace in the step (4) is a tube furnace, and the inert gas comprises argon, helium and nitrogen; the temperature rising rate is 1-3 ℃ for min -1 。
Another aspect of the present invention provides the 3D structure Fe/Fe prepared by the above preparation method 3 C@FeNC difunctional oxygen electrocatalyst.
The invention also provides the Fe/Fe with the 3D structure 3 The application of the C@FeNC difunctional oxygen electrocatalyst in fuel cells and metal-air cells.
Compared with the prior art, the invention has the following beneficial effects:
(1) Using Fe assembled from nanorods 2 O 3 The hollow microsphere is used as a template, and Fe is obtained after dopamine in-situ polymerization 2 O 3 The PDA can replicate the microscopic morphology of the template to form a hollow porous open framework, and the large pore channels and the high specific surface area of the PDA can expose more active sites, can promote mass transfer of reactants, intermediates and products, and are beneficial to improving the ORR/OER catalytic activity of the material.
(2) After the iron-based nano particles are coated by the nitrogen doped carbon, the oxidation agglomeration of the iron-based nano particles and the dissolution in a strong alkali environment are avoided, so that the catalyst has good stability. Meanwhile, the iron agent nano particles enrich the electron density of the carbon surface, promote the surface reaction, and further improve the electrocatalytic activity of the material.
(3) In the template Fe 2 O 3 And nitrogen-rich precursor g-C 3 N 4 The intermediate introduction of polydopamine layer slows down g-C 3 N 4 With Fe 2 O 3 Thereby protecting the morphology of the template, i.e. the structure of the template is protected while the nitrogen content is increased, and in addition, in the pyrolysis process, nitrogen atoms and Fe atoms form Fe-N X The ligand, the active site of the ORR reaction.
(4) The presence of iron-based nanoparticles promotes Fe/Fe 3 OER performance of c@fenc.
(5) The Fe/Fe of the invention 3 The ORR and OER activity/stability and methanol resistance of the c@fenc catalyst under alkaline conditions are superior to commercial noble metal catalysts.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described.
Fig. 1 is an XRD pattern of the samples prepared in example 2, example 11 and example 12.
FIG. 2 is an SEM image of samples prepared in example 2, example 11 and example 12; wherein a is Fe in example 2 2 O 3 SEM images of @ PDA, b, c and d are SEM images of samples calcined in example 2, example 11 and example 12, respectively.
FIG. 3 is an XPS chart of the samples prepared in example 2, example 11, and example 12.
FIG. 4 shows the results of example 2, example 11, example 12 and comparative example 1 at O 2 ORR performance LSV curve in saturated 0.1M KOH electrolyte.
FIG. 5 shows the results of example 2, example 11, example 12 and comparative example 2 at O 2 OER performance LSV curve in saturated 1m koh electrolyte.
FIG. 6 shows the results of examples 1, 2, 3, 4 and 5Preparation of samples at O 2 ORR performance LSV curve in saturated 0.1M KOH electrolyte.
FIG. 7 shows the samples prepared in example 1, example 2, example 3, example 4 and example 5 at O 2 OER performance LSV curve in saturated 1M KOH electrolyte.
FIG. 8 shows the samples prepared in example 2, example 6, example 7, example 8, example 9 and example 10 at O 2 ORR performance LSV curve in saturated 0.1M KOH electrolyte.
FIG. 9 shows the samples prepared in example 2, example 7, example 8, example 9 and example 10 at O 2 OER performance LSV curve in saturated 1M KOH electrolyte.
FIG. 10 is the sample of example 2 and comparative example 1 at O 2 Chronoamperometric curve in saturated 0.1M KOH electrolyte.
Fig. 11 is a graph of test results of the sample of example 2 in the metal-air battery of example 13.
Detailed Description
The following detailed description of the invention is provided in connection with examples, but the implementation of the invention is not limited thereto, and it is obvious that the examples described below are only some examples of the invention, and that it is within the scope of protection of the invention to those skilled in the art to obtain other similar examples without inventive faculty.
Example 1:
Fe/Fe with 3D structure 3 The preparation method of the C@FeNC difunctional oxygen electrocatalyst comprises the following steps:
(1) 0.4mmol of Fe (NO) 3 ) 3 ·9H 2 O was dissolved in a mixed solution of 60ml of glycerol and 420ml of isopropanol until Fe (NO 3 ) 3 ·9H 2 After O is completely dissolved, 6ml of deionized water is added, stirred for 15min, poured into a high-temperature reaction kettle and reacted for 12h at 190 ℃. Washing with ethanol and deionized water for several times, drying at 60deg.C, transferring into a tube furnace, heating to 400deg.C under air atmosphere, maintaining for 3 hr at a heating rate of 1deg.C for min -1 Obtaining 3D Fe 2 O 3 A microsphere;
(2) 100mg Fe 2 O 3 Dispersing microsphere in 75ml water, magnetically stirring for 1 hr to form uniform suspension, adding 25mg of tris (hydroxymethyl) aminomethane and 75mg of dopamine into the suspension, magnetically stirring for 6 hr, centrifugally washing for several times, and drying at 60deg.C to obtain Fe 2 O 3 @PDA；
(3) Adding melamine or urea into quartz boat, placing in tube furnace, heating to 550deg.C under air, and heating at 6deg.C for 6 min -1 Preserving heat for 4h to obtain g-C 3 N 4 ；
(4) Fe is added to 2 O 3 @ PDA with g-C 3 N 4 According to the mass ratio of 1:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.5h at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC。
Example 2:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 1:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.75 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC。
Example 3:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 1:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 1 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-1。
Example 4:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 1:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 2 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-2。
Example 5:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 1:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 3 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-3。
Example 6:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 50:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.75 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-50/1。
Example 7:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 20:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.75 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-20/1。
Example 8:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 10:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.75 hr at 2 deg.C for min -1 Fe/Fe3C@FeNC-10/1 is obtained.
Example 9:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 1:1.5 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.75 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-1/1.5。
Example 10:
this example is identical to the experimental procedure of example 1, except that: fe (Fe) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio is 1:2 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.75 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-1/2。
Example 11:
this example is identical to the experimental procedure of example 1, except that: fe is added to 2 O 3 Directly with g-C 3 N 4 The mass ratio is 1:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.75 hr at 2 deg.C for min -1 Obtaining Fe/Fe 3 C@FeNC-nP-1/1。
Example 12:
adding 25mg of tris (hydroxymethyl) aminomethane and 75mg of dopamine into 75ml of water, magnetically stirring for 6h, centrifugally washing for several times, drying at 60 ℃ to obtain PDA, and mixing the PDA with g-C 3 N 4 According to the mass ratio of 1:1 grinding uniformly, transferring into a tube furnace, N 2 Heating to 650 deg.C under atmosphere, maintaining for 0.5h at 2 deg.C for min -1 NC is obtained.
Example 13:
the metal-air battery of this embodiment is a zinc-air battery, comprising an air diffusion electrode/electrolyte and a metal electrode; the air diffusion electrode is prepared into 3D hollow Fe/Fe 3 Dispersing the C@FeNC material in isopropanol to prepare a dispersion liquid, coating the dispersion liquid on carbon cloth, and naturally drying to obtain the carbon cloth; 3D hollow Fe/Fe 3 The loading capacity of the C@FeNC material on the carbon cloth is 1.0mg cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte is 0.2M zinc acetate and 6M aqueous solution of potassium hydroxide; the metal electrode is a polished zinc plate.
Comparative example 1:
the experiment of this example is identical to that of example 13, except that a commercial 20% Pt/C catalyst is used.
Comparative example 2:
the experiments of this example are identical to those of example 13, except that commercial IrO is used 2 A catalyst.
FIG. 1 is XRD patterns of samples prepared in example 2, example 11 and example 12; as can be seen from the figure, both example 2 and example 11 present diffraction peaks for elemental iron and iron carbide.
FIG. 2 is an SEM image of samples prepared in example 2, example 11 and example 12; wherein a is Fe in example 2 2 O 3 SEM images of @ PDA, b, c and d are SEM images of example 2, example 11 and example 12, respectively, after calcination; as can be seen from the figure, fe 2 O 3 The @ PDA is a hollow microsphere assembled from nanorods; as is clear from SEM images of fig. 2b, c, when no dopamine is added, the microsphere structure of the template is destroyed after pyrolysis to form individual nanorods, and the 3D structure of the template is preserved after dopamine coating; from figure d it can be seen that PDA and g-C 3 N 4 The nanosphere structure of the PDA remains after pyrolysis at high temperature.
FIG. 3 is an XPS chart of the samples prepared in example 2, example 11, and example 12. FIG. 3a shows the XPS spectrum of example 2, example 11, example 12, FIG. 3b shows the Fe 2p high-resolution spectrum of example 2, example 11, wherein 706.1, 720.1eV is Fe 0 Is Fe with 723.2eV as peak 709.3 2+ Is a peak of (2); FIG. 3c is an N1s high resolution spectrum of example 2, example 11, example 12, wherein example 2, example 11, can deconvolve well four peaks at 397.8, 398.8, 399.9 and 4002eV, respectively attributed to pyridine N, fe-N X Pyrrole N and graphite N; while example 12 has no Fe-N X The method comprises the steps of carrying out a first treatment on the surface of the Fig. 3d shows the relative content of N in example 2, example 11 and example 12.
FIG. 4 shows the results of example 2, example 11, example 12 and comparative example 1 at O 2 ORR performance LSV curve in saturated 0.1M KOH electrolyte. As can be seen, example 2 has the best ORR performance with a half-wave potential of 0.83V and a current density of 7.7mA cm -2 。
Fig. 5 is a diagram of example 2, example 11,samples prepared in example 12 and comparative example 2 were prepared at O 2 OER performance LSV curve in saturated 1m koh electrolyte. From FIG. 5 it can be seen that example 2 has an optimal OER performance of 10mA cm -2 The corresponding voltage is the smallest (1.45V).
FIG. 6 shows the samples prepared in example 1, example 2, example 3, example 4 and example 5 at O 2 ORR performance LSV curve in saturated 0.1M KOH electrolyte at a sweep rate of 10mV s -1 Rotational speed: 1600rpm, room temperature; as can be seen from FIG. 6, the material has the best ORR performance at a calcination time of 0.75h, a half-wave potential of 0.83V and a current density of 7.7mA cm -2 。
FIG. 7 shows the samples prepared in example 1, example 2, example 3, example 4 and example 5 at O 2 OER performance LSV curve in saturated 1M KOH electrolyte at a sweep rate of 10mV s -1 Rotational speed: 1600rpm, room temperature; as can be seen from FIG. 7, at a calcination time of 0.75h, there is an optimum OER performance of 10mA cm -2 The corresponding voltage is the smallest (1.45V).
FIG. 8 shows the samples prepared in example 2, example 6, example 7, example 8, example 9 and example 10 at O 2 ORR performance LSV curve in saturated 0.1M KOH electrolyte at a sweep rate of 10mV s -1 Rotational speed: 1600rpm, room temperature. It can be seen from FIG. 8 that as Fe 2 O 3 @ PDA with g-C 3 N 4 The half-wave potential increases and then decreases. At Fe 2 O 3 @ PDA with g-C 3 N 4 The mass ratio of (2) is 1:1, has the best ORR performance, the half-wave potential of 0.83V and the current density of 7.7mA cm -2 。
FIG. 9 shows the results of examples 2, 7, 8, 9 and 10 at O 2 OER performance LSV curve in saturated 1M KOH electrolyte at a sweep rate of 10mV s -1 Rotational speed: 1600rpm, room temperature. It can be seen from FIG. 8 that as Fe 2 O 3 @ PDA with g-C 3 N 4 Is increased by a mass ratio of 10mA cm -2 The corresponding voltage is reduced and then increased; at Fe 2 O 3 @ PDA with g-C 3 N 4 The mass ratio of (2) is 1:1, has the best OER performance of 10mA cm -2 The corresponding voltage is the smallest (1.45V).
FIG. 10 is the sample of example 2 and comparative example 1 at O 2 The current curve was measured in saturated 0.1M KOH electrolyte at 0.60V (vs RHE) at room temperature. As can be seen from FIG. 10, the Pt/C catalyst decays to 64% of the original after 18000s cycle, while Fe/Fe 3 C@FeNC decreased by only 6%, indicating Fe/Fe 3 The stability of C@FeNC is obviously better than that of Pt/C catalyst, which shows that 3D Fe/Fe coated by nitrogen-doped carbon 3 The C@FeNC catalyst has excellent catalytic stability.
FIG. 11 is a graph showing the test results of the sample of example 2 on the metal-air battery of example 13, wherein a is a schematic diagram of a rechargeable zinc-air battery, b is the open circuit potential of the zinc-air battery, c is the charge-discharge polarization curve and its corresponding power density, and d is the use of Fe/Fe 3 Specific cell capacity and energy density of C@FeNC, (e) from Fe/Fe 3 C@FeNC assembled rechargeable zinc-air cell with current density of 5mA cm -2 Discharge-charge cycle curve at that time.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (8)

1. Fe/Fe with 3D structure 3 The preparation method of the C@FeNC difunctional oxygen electrocatalyst is characterized by mainly comprising the following steps of:
(1) Preparation of Fe 2 O 3 Microspheres: dispersing ferric salt into a solvent, transferring the mixed solution into a reaction container, reacting for 6-24 hours at 160-220 ℃, washing, drying, heating to 350-450 ℃ in air atmosphere, and preserving heat for 2-5 hoursh, obtaining Fe with 3D structure 2 O 3 A microsphere;
(2) Preparation of Fe 2 O 3 @ PDA: fe prepared in the step (1) 2 O 3 Dispersing the microspheres in deionized water, adding tris (hydroxymethyl) aminomethane and dopamine, and stirring for reacting 2-10h to obtain Fe 2 O 3 PDA material;
(3) Preparation of g-C 3 N 4 : heating melamine or urea to 500-600 ℃ in an air atmosphere, and preserving heat for 2-6 h to obtain g-C 3 N 4 ；
(4) Preparation of Fe/Fe 3 C@fenc microsphere catalyst: fe obtained in the step (2) 2 O 3 @ PDA with g-C prepared in step (3) 3 N 4 Grinding and mixing, placing in a reaction furnace, heating to 600-700 ℃ under inert atmosphere, and calcining for 0.5-3 h to obtain Fe/Fe 3 C@FeNC difunctional oxygen electrocatalyst;
the ferric salt in the step (1) comprises ferric nitrate, ferric sulfate and ferric chloride; the concentration of the ferric salt is 0.01-1 mM, and the solvent is a mixed solution of glycerol, isopropanol and deionized water;
the volume ratio of the glycerol, the isopropanol and the deionized water is (5-10): (60-80): 1.
2. the process according to claim 1, wherein the reaction vessel in step (1) is a high-pressure reactor; the washing is to sequentially use alcohol and deionized water for 2-5 times; the temperature rising rate is 1-3 ℃ for min -1 。
3. The process according to claim 1, wherein Fe in the step (2) 2 O 3 The mass ratio of the microsphere to the deionized water is (0.5-2): 1, fe 2 O 3 The mass ratio of the microsphere to the tris (hydroxymethyl) aminomethane to the dopamine is (2-6): 1: (2-4).
4. The preparation method according to claim 1, wherein the specific step of the step (3) isAdding melamine or urea into a quartz boat, placing the quartz boat into a tube furnace, and heating to 500-600 ℃ in an air atmosphere at a heating rate of 3-6 ℃ for min -1 Preserving heat for 2-6 hours.
5. The method according to claim 1, wherein the Fe in the step (4) 2 O 3 @ PDA with g-C 3 N 4 The mass ratio of (1) to (50:1) is equal to (1:2).
6. The method according to claim 1, wherein the reaction furnace in the step (4) is a tube furnace, and the inert atmosphere comprises argon, helium and nitrogen; the temperature rising rate is 1-3 ℃ for min -1 。
7. The 3D structure Fe/Fe prepared by the method of any one of claims 1-6 3 C@FeNC difunctional oxygen electrocatalyst.
8. The 3D structure Fe/Fe of claim 7 3 The application of the C@FeNC difunctional oxygen electrocatalyst in fuel cells or/and metal-air cells.
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