CN110729485A - Preparation method and application of porous carbon-coated PdFe/C alloy nano-frame - Google Patents

Preparation method and application of porous carbon-coated PdFe/C alloy nano-frame Download PDF

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CN110729485A
CN110729485A CN201910868195.4A CN201910868195A CN110729485A CN 110729485 A CN110729485 A CN 110729485A CN 201910868195 A CN201910868195 A CN 201910868195A CN 110729485 A CN110729485 A CN 110729485A
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naphthylamine
pdfe
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complex
porous carbon
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周建成
江娴
李乃旭
葛阳
付更涛
唐亚文
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Southeast University
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • 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
    • 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation method and application of a porous carbon coated PdFe/C alloy nano-frame. The preparation method comprises the following steps: with 1-naphthylamine (C)10H9N) as complexing agent with PdCl2Formation of Pd (II) - (C)10H7‑NH2) The flaky yellow precipitated complex is placed in FeCl3Is ultrasonically mixed in the aqueous solution of (1) and stirred for a long time to sufficiently adsorb Fe on the surface of the flaky precipitate3+The obtained Pd (II)/Fe (III) - (C)10H7‑NH2) And (3) placing the flaky yellowish green precipitate in an inert atmosphere for high-temperature heat treatment to obtain the PdFe/C alloy nano frame coated with the porous carbon. The carbon-coated porous PdFe/C prepared by the inventionThe alloy nano-frame has the advantages of superfine PdFe alloy particle size, adjustable composition, high electrochemical activity and stability, simple preparation process, convenience for batch production, environmental friendliness and the like, and shows higher electrocatalytic activity and stability when being used as a cathode oxygen reduction catalyst under an acidic condition.

Description

Preparation method and application of porous carbon-coated PdFe/C alloy nano-frame
Technical Field
The invention relates to a preparation method of a porous carbon coated PdFe/C alloy nano-frame with high electrochemical activity and stability.
Background
Energy shortage and environmental pollution have caused high attention of the current society, and the development of renewable clean energy power generation and the electric automobile industry has important strategic significance. Low temperature polymer electrolyte membrane fuel cells and metal-air cells are expected to form efficient, clean energy storage and conversion systems due to their high energy conversion efficiency, low pollution, safety, and low cost. The Oxygen Reduction Reaction (ORR) is an important cathode reaction in fuel cells and metal air cells. Currently, the conventional ORR catalyst is a noble metal Pt-based catalyst, and the cost accounts for about 50% of the total cost of the fuel cell, which seriously hinders the commercialization of the fuel cell and the metal-air battery. The area specific activity of an ideal ORR catalyst at 0.9V (vs. NHE) needs to reach 180mA cm-2. In order to reduce the cost of the catalyst, how to synthesize a catalyst having a high initial potential, a high current density, and a high stability has become a hot spot of research in recent years.
Pd has many similar properties (same family, same crystal structure, similar atomic size in the periodic table) to Pt, and is relatively inexpensive compared to Pt, and has attracted great interest as an efficient oxygen reduction nanocatalyst. In recent years, researches show that the addition of other transition metals such as Fe, Co, Ni and the like into Pd can cause the contraction of Pd-Pd bonds, thereby changing the electronic structure of Pd and causing the center of the d-band to move downwards. The electronic structure change can make OH intensively adsorbed on the doped transition metal to optimize the strength of Pd-O bond, thereby improving the performance of catalyzing ORR by the Pd-based catalyst. Generally, this structural transformation requires high temperature annealing (>500 ℃) to be achieved, but inevitably leads to aggregation and growth of nanoparticles during high temperature preparation, with consequent reduction in the specific activity of the catalyst. Therefore, in designing and optimizing the catalyst, great efforts are made to reduce the particle size as much as possible in order to prevent the catalyst from agglomerating during annealing. One effective method is to form a surface protective coating such as a carbon shell, an oxide shell, an inorganic barrier layer, a graphitized hollow sphere and the like on the surface of the metal particle. However, the presence of a protective layer can also block the active sites to some extent, reducing the mass transfer rate and thus the catalytic performance. Thus, the need to coat the protective shell thin enough to block the active sites is a very delicate and difficult to handle process. Therefore, it is necessary to explore a convenient and feasible strategy for protecting the shell layer to prevent the agglomeration of the nanoparticles without affecting the electrocatalytic performance of the nanoparticles.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problems, the invention aims to provide a preparation method of a porous carbon coated PdFe/C alloy nano-framework and application of a catalyst prepared by the method in cathode oxygen reduction electrocatalysis in an acid electrolyte. According to the invention, the superfine and PdFe alloy nano-particles uniformly dispersed porous PdFe/C frame structure coated by the ultrathin carbon layer is prepared by carbonizing a pre-generated yellow-green sheet Pd (II) Fe (III) -naphthylamine complex with Fe (III) adsorbed on the surface at high temperature, so that the catalytic activity of the catalyst is effectively improved, and the catalyst has extremely high structural stability.
The technical scheme is as follows: the preparation method of the porous carbon coated PdFe/C alloy nano frame adopts the following technical scheme:
PdCl2Aqueous solution and 1-naphthylamine (C)10H9N) ethanol solution is fully mixed to form flake Pd (II) - (C)10H7-NH2) The yellow complex precipitates and is placed in FeCl3Adsorbing Fe (III) in the water-ethanol mixed solution to generate yellow green sheet Pd (II)/Fe (III) - (C)10H7-NH2) Yellow colourAnd precipitating a green complex, centrifugally drying, placing solid powder in an inert atmosphere for high-temperature calcination, and cooling to obtain the porous carbon coated PdFe/C alloy nano-frame.
The method comprises the following steps:
1) synthesis of yellow flaky pd (ii) -naphthylamine complex: taking naphthylamine (C)10H9N), dissolving in ethanol, adding PdCl2Fully ultrasonically mixing the aqueous solution, standing to obtain yellow flaky Pd (II) -naphthylamine complex precipitate, and centrifuging to remove supernatant;
2) synthesizing a yellow-green flaky Pd (II)/Fe (III) -naphthylamine complex: the obtained yellow flaky Pd (II) -naphthylamine complex precipitate is placed in FeCl3Stirring overnight after sufficient ultrasonic dispersion in the aqueous ethanol mixed solution to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifuging and drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: and (3) heating the yellow-green flaky Pd (II)/Fe (III) -naphthylamine complex prepared in the step 2) to 300-1000 ℃ in an inert atmosphere, carrying out heat treatment, keeping the temperature for 0.5-24 h, and then cooling to obtain the final product, namely the porous carbon-coated PdFe/C alloy nano-frame.
In the preparation of the yellow flaky Pd (II) -naphthylamine complex, the dosage ratio of Pd (II) to 1-naphthylamine is 0.01-99.99%.
The FeCl3The water-ethanol mixed solution of (1), wherein the volume ratio of water to ethanol is (0.1-99): 1.
The Pd (II)/Fe (III) -naphthylamine complex has the following components: the material dosage ratio of Fe is (0.1-99): 1.
The time for adsorbing Fe (III) by the Pd (II) -naphthylamine complex is 0.5-120 h.
The inert atmosphere is nitrogen, argon or carbon dioxide atmosphere.
Under the inert atmosphere, the temperature programming rate is 2.5-20 ℃ per minute-1。
In the porous frame structure, the superfine PdFe alloy nano particles are uniformly coated and fixed in the porous carbon frame by the ultrathin carbon layer.
The material prepared by the preparation method of the porous carbon-coated PdFe/C alloy nano-frame is applied to a catalyst for reducing the cathode oxygen of a fuel cell in an acidic electrolyte.
In the method of the invention, PdCl is used21-naphthylamine is taken as a complex as a metal source, a flaky Pd (II) -naphthylamine complex is formed by coordination and complexation in advance, and then Fe (III) is fully adsorbed on the surface of the flaky Pd (II) -naphthylamine complex by taking the flaky Pd (II) -naphthylamine complex as a template to form Pd (II)/Fe (III) - (C)10H7-NH2) And (3) performing yellow-green flaky precipitation, and preparing the porous carbon coated PdFe/C alloy nano frame by high-temperature carbonization self-reduction in further inert atmosphere. The PdFe alloy nanoparticles obtained in the catalyst have superfine particle sizes and are uniformly distributed in the porous carbon nano frame, the coating of the ultrathin carbon layer does not affect the catalytic activity of the PdFe particles, the nanoparticles can be effectively fixed, the further growth and aggregation of the nanoparticles are prevented, and the catalyst is endowed with higher structural stability and catalytic stability.
The PdFe/C alloy nano-frame coated with the porous carbon prepared by the invention has the following advantages that the ① porous frame structure is beneficial to mass transfer in the electrocatalytic reaction process, the formed ultrafine (-6.0 nm) and uniform PdFe alloy nano-particles are beneficial to providing more electrocatalytic active sites, the doping of N element in ② porous carbon frame is beneficial to improving the electronic structure of carbon carrier to provide more active sites and the graphitization degree of the carbon frame, the PdFe alloy nano-particles formed by introducing ③ Fe are beneficial to improving the Pd electronic structure so as to improve the electrocatalytic activity of Pd, and the ④ ultrathin carbon layer coated structure effectively prevents the aggregation and dissolution of Pd nano-particles so as to improve the sintering resistance and electrochemical stability of the Pd nano-particles.
Has the advantages that: compared with the prior art, the invention has the advantages that:
the invention relates to a preparation method of a cathode oxygen reduction catalyst in an acidic electrolyte, and a two-dimensional porous carbon-coated PdFe/C alloy nano-frame is prepared by a high-temperature carbonization self-reduction method which is simple and convenient and can realize large-scale production. The selected complex 1-naphthylamine is cheap and easy to obtain, the method has simple and feasible process, easily controlled reaction conditions, low cost and simple equipment, and can realize large-scale production; the PdFe alloy nano particles are superfine in particle size and uniform in size and are embedded into a porous carbon nano frame, so that the prepared catalyst is efficient and stable, long in service life, and has the characteristics of multiple active sites, high electro-catalytic activity, porosity and the like. Compared with a commercial 20% Pd/C catalyst purchased from Johnson Matthey company and a porous Pd/C nano-frame not doped with Fe, the prepared porous carbon-coated PdFe/C alloy nano-frame has more excellent oxygen reduction electrocatalytic performance and stability in an acid electrolyte, is a fuel cell catalyst with great potential, and has wide application prospect in the future energy industry.
The present invention will be described in detail with reference to specific examples. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
Drawings
FIG. 1 is a low magnification TEM spectrum of a yellowish green flaky Pd (II)/Fe (III) -naphthylamine complex prepared according to the method of the present invention.
FIG. 2 is PdCl2Aqueous solution of FeCl3Aqueous solution, 1-naphthylamine ethanol solution and PdCl2With FeCl3And the ultraviolet-visible spectrum after complexation with 1-naphthylamine.
FIG. 31 is an IR spectrum of a complex of naphthylamine with yellow-green sheet Pd (II)/Fe (III) -naphthylamine.
FIG. 4 is TEM image of the porous carbon coated PdFe/C alloy nano-framework prepared by the method of the invention under different times and the particle size distribution diagram of PdFe alloy nano-particles.
FIG. 5 is a comparative XRD spectrum of a porous carbon coated PdFe/C alloy nano-framework prepared by the method of the present invention and a porous Pd/C framework obtained without adding Fe element.
FIG. 6 is an EDX spectrum of a porous carbon coated PdFe/C alloy nano-frame prepared according to the method of the present invention.
FIG. 7 is an oxygen electrocatalytic reduction (ORR) curve of a porous carbon coated PdFe/C alloy nano-framework prepared according to the method of the present invention compared to a porous Pd/C framework and a commercial 20% Pd/C.
FIG. 8 is a stability chronoamperometric test curve of porous carbon coated PdFe/C alloy nano-frameworks prepared according to the method of the present invention compared to porous Pd/C frameworks and commercial 20% Pd/C.
Detailed Description
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps: PdCl2Aqueous solution and 1-naphthylamine (C)10H9N) ethanol solution is fully mixed to form flake Pd (II) - (C)10H7-NH2) The yellow complex precipitates and is placed in FeCl3Adsorbing Fe (III) in the water-alcohol mixed solution to generate yellow green sheet Pd (II)/Fe (III) - (C)10H7-NH2) And (3) precipitating a complex, centrifugally drying, placing solid powder in an inert atmosphere, calcining at high temperature, and cooling to obtain the carbon-coated porous PdFe/C alloy nano-frame.
More specifically, the preparation method of the porous carbon-coated PdFe/C alloy nano-frame specifically comprises the following steps:
1) synthesizing yellow flaky Pd (II) -naphthylamine complex by weighing a certain amount of naphthylamine (C)10H9N), dissolving in ethanol, adding PdCl2Fully ultrasonically mixing the aqueous solution, standing to obtain yellow flaky Pd (II) -naphthylamine complex precipitate, and centrifuging to remove supernatant;
2) synthesizing a yellow-green flaky Pd (II)/Fe (III) -naphthylamine complex: the resulting yellow precipitate was placed in FeCl3Stirring overnight after sufficient ultrasonic dispersion in the aqueous ethanol mixed solution to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifuging and drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: and (3) carrying out programmed heating on the yellowish green powder prepared in the step 2) to 300-1000 ℃ in an inert atmosphere for heat treatment, keeping the temperature for 0.5-24 h, and then cooling to obtain a final product.
Preferably, the feeding ratio of Pd (II) to 1-naphthylamine in the preparation of the yellow flaky Pd (II) -naphthylamine complex is 0.01-99.99%.
The FeCl3The ratio of water to ethanol in the solvent is (0.1-99): 1.
The Pd (II)/Fe (III) -naphthylamine complex has the following components: the feeding ratio of Fe is (0.1-99): 1.
The time for adsorbing Fe (III) by the Pd (II) -naphthylamine complex is 0.5-120 h.
The inert atmosphere is nitrogen, argon or carbon dioxide atmosphere.
Under the inert atmosphere, the temperature programming rate is 2.5-20 ℃ per minute-1。
The material prepared by the preparation method is of a porous frame structure, and the superfine PdFe alloy nanoparticles are uniformly coated and fixed in the porous carbon frame by the ultrathin carbon layer. The material can be applied as a catalyst for fuel cell cathode oxygen reduction in acid electrolytes.
The technical solutions of the present invention are further described in detail by the following specific examples, but it should be noted that the following examples are only used for describing the content of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: will step withThe yellow-green powder prepared in the step 2) is heated for 5 min at the programmed heating rate in the nitrogen atmosphere-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 2
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 0.286mg of naphthylamine (C) is weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 3
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 2.86g of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic waves to enable the mixture to be flakyFully adsorbing Fe (III) by 1-naphthylamine molecules on the surface of the Pd (II) -naphthylamine complex, and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 4
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 0.1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 5
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesis of a yellowish green sheet Pd (II)/Fe (III) -naphthylamine ComplexPlacing the obtained yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 99: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 6
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 40ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 7
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 0.04ml0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 8
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 0.5h after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 9
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) yellow sheetPreparation of pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 120h after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 10
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in an argon atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 11
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is heated for 5 min at the programmed heating rate in the carbon dioxide atmosphere-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 12
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: putting the yellow-green powder prepared in the step 2) in a nitrogen atmosphereAt a programmed temperature rate of 5 ℃ for min-1Heating to 300 deg.C, maintaining at the temperature for 6h, and cooling to obtain final product.
Example 13
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 1000 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 14
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex are filledAdsorbing Fe (III) and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 0.5h, and cooling to obtain final product.
Example 15
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 24 hr, and cooling to obtain final product.
Example 16
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 2.5 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
Example 17
The preparation method of the porous carbon-coated PdFe/C alloy nano-frame comprises the following steps:
1) preparation of yellow flaky pd (ii) -naphthylamine complex: 286mg of naphthylamine (C) are weighed out10H9N) dissolving in 4mL of ethanol, and fully performing ultrasonic treatment to dissolve; 4mL of 0.05mol L was added-1PdCl of (2)2Standing the aqueous solution to obtain a yellow flaky Pd (II) -naphthylamine complex, and centrifugally drying;
2) synthesizing yellow green sheet Pd (II)/Fe (III) -naphthylamine complex by placing the yellow precipitate in 4ml of 0.05mol L-1FeCl3The volume ratio of the water to the ethanol is 1: 1, stirring for 24 hours after fully and uniformly dispersing by ultrasonic to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifugally drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: the yellow green powder prepared in the step 2) is put in nitrogen atmosphere at the programmed heating rate of 20 ℃ for min-1Heating to 600 deg.C, maintaining at the temperature for 6 hr, and cooling to obtain final product.
The porous carbon-coated PdFe/C alloy nano-framework prepared in the embodiment and the precursor Pd (II)/Fe (III) -naphthylamine complex thereof are characterized by adopting paths such as TEM, HRTEM, UV-vis, FT-IR, XRD, EDX and the like. The homogeneous two-dimensional sheet structure of the precursor can be clearly observed from the low-magnification TEM (figure 1), and the ultraviolet spectrum (figure 2) and the infrared spectrum (figure 3) both show that the 1-naphthylamine has stronger coordination with Pd (II) and Fe (III), thereby promoting the successful formation of the yellow-green sheet Pd (II)/Fe (III) -naphthylamine complex. Further analyzing the structure composition of the porous carbon-coated PdFe/C alloy nano-framework by TEM and HRTEM (figure 4), clearly showing the uniform porous framework structure of the obtained product from figure 4, and further enlarging the HRTEM image shows that PdFe alloy nano-particles are uniformly embedded in the porous framework and have the particle size of about 6.34 nm. From fig. 5, the XRD spectrum can further show that, compared with the porous Pd/C framework obtained without Fe element, the PdFe/C alloy nano framework has a certain shift in peak position, corresponding to the phase of PdFe alloy, further demonstrating the successful reduction of Pd and Fe and the successful preparation of PdFe/C alloy nano framework. FIG. 5 is an EDX spectrum of the PdFe/C alloy nano-framework prepared, from which it can be seen that the atomic ratio of Pd to Fe in the catalyst is 76.6: 23.4, close to 3: 1. finally, the prepared porous carbon-coated PdFe/C alloy nano-frame was applied to the electrocatalytic reduction of cathode oxygen in acidic electrolytes with commercial 20% Pd/C and porous Pd/C nano-frames as reference catalysts. Fig. 7 and 8 are comparisons of the activity and stability of the two catalysts, respectively, and it can be seen from fig. 7 that the porous carbon coated PdFe/C alloy nano-framework has the best oxygen reduction electrocatalytic activity. After 10000s of timing current test, the oxygen reduction activity loss of the porous carbon coated PdFe/C alloy nano-framework is minimum, while the oxygen reduction activity of the commercial Pd/C catalyst is almost inactivated, which is mainly attributed to that the carbon coated structure of the prepared catalyst effectively prevents the dissolution and agglomeration of PdFe alloy nano-particles.

Claims (10)

1. A preparation method of a porous carbon coated PdFe/C alloy nano-frame is characterized by comprising the following steps: PdCl2Aqueous solution and 1-naphthylamine (C)10H9N) ethanol solution is fully mixed to form flake Pd (II) - (C)10H7-NH2) The yellow complex precipitates and is placed in FeCl3Adsorbing Fe (III) in the water-ethanol mixed solution to generate yellow green sheet Pd (II)/Fe (III) - (C)10H7-NH2) Precipitating with yellow-green complex, centrifuging, drying, calcining the solid powder at high temperature in inert atmosphere, and cooling to obtain the final productThe porous carbon-coated PdFe/C alloy nano-framework.
2. The method for preparing the porous carbon coated PdFe/C alloy nano-frame according to claim 1, wherein the method comprises the following steps:
1) synthesis of yellow flaky pd (ii) -naphthylamine complex: taking naphthylamine (C)10H9N), dissolving in ethanol, adding PdCl2Fully ultrasonically mixing the aqueous solution, standing to obtain yellow flaky Pd (II) -naphthylamine complex precipitate, and centrifuging to remove supernatant;
2) synthesizing a yellow-green flaky Pd (II)/Fe (III) -naphthylamine complex: the obtained yellow flaky Pd (II) -naphthylamine complex precipitate is placed in FeCl3Stirring overnight after sufficient ultrasonic dispersion in the aqueous ethanol mixed solution to ensure that 1-naphthylamine molecules on the surface of the flaky Pd (II) -naphthylamine complex fully adsorb Fe (III), and centrifuging and drying;
3) preparing a porous carbon-coated PdFe/C alloy nano-frame: and (3) heating the yellow-green flaky Pd (II)/Fe (III) -naphthylamine complex prepared in the step 2) to 300-1000 ℃ in an inert atmosphere, carrying out heat treatment, keeping the temperature for 0.5-24 h, and then cooling to obtain the final product, namely the porous carbon-coated PdFe/C alloy nano-frame.
3. The preparation method of the porous carbon coated PdFe/C alloy nano-framework as claimed in claim 2, wherein the dosage ratio of Pd (II) and 1-naphthylamine in the preparation of the yellow flaky Pd (II) -naphthylamine complex is 0.01-99.99%.
4. The method for preparing the porous carbon coated PdFe/C alloy nano-frame according to claim 2, wherein the FeCl is3The water-ethanol mixed solution of (1), wherein the volume ratio of water to ethanol is (0.1-99): 1.
5. The method for preparing the porous carbon coated PdFe/C alloy nano-framework according to claim 2, wherein the Pd (II)/Fe (III) -naphthylamine complex comprises Pd: the material dosage ratio of Fe is (0.1-99): 1.
6. The preparation method of the porous carbon-coated PdFe/C alloy nano-frame according to claim 2, wherein the time for adsorbing Fe (III) by the Pd (II) -naphthylamine complex is 0.5-120 h.
7. The method for preparing the porous carbon coated PdFe/C alloy nano-frame according to claim 2, wherein the inert atmosphere is nitrogen, argon or carbon dioxide.
8. The preparation method of the porous carbon-coated PdFe/C alloy nano-frame according to claim 2, characterized in that the programmed heating rate is 2.5-20 ℃ min in the inert atmosphere-1。
9. The preparation method of the porous carbon-coated PdFe/C alloy nano-frame according to any one of claims 1 to 8, wherein the porous frame structure, the ultra-fine PdFe alloy nano-particles are uniformly coated and fixed in the porous carbon frame by the ultra-thin carbon layer.
10. A material prepared by the preparation method of the porous carbon coated PdFe/C alloy nano-frame according to any one of claims 1 to 8 is applied to a catalyst for reducing the cathode oxygen of a fuel cell in an acid electrolyte.
CN201910868195.4A 2019-09-12 2019-09-12 Preparation method and application of porous carbon-coated PdFe/C alloy nano-frame Pending CN110729485A (en)

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