CN110224148B - Pt or Au modified porous PdFe intermetallic compound and preparation method and application thereof - Google Patents

Pt or Au modified porous PdFe intermetallic compound and preparation method and application thereof Download PDF

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CN110224148B
CN110224148B CN201910440841.7A CN201910440841A CN110224148B CN 110224148 B CN110224148 B CN 110224148B CN 201910440841 A CN201910440841 A CN 201910440841A CN 110224148 B CN110224148 B CN 110224148B
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CN110224148A (en
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王得丽
龚明星
申涛
邓智平
杨弘毅
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Huazhong 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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 a Pt or Au modified porous PdFe intermetallic compound and a preparation method and application thereof, belonging to the technical field of electrochemistry. The intermetallic compound is a nano particle, the inner core of the nano particle is an ordered PdFe intermetallic compound, the surface of the nano particle is a porous structure with Pd uniformly distributed, and the surface of the porous structure is modified with Pt or Au. The preparation method comprises the steps of using palladium acetate and ferric salt as metal sources, loading the metal sources on a carbon carrier, thermally decomposing acetate in a protective atmosphere to obtain a loaded PdFe intermetallic compound, etching Fe on the surface, and preparing the Pt or Au modified PdFe intermetallic compound with porous surface and ordered kernel by adopting a surface modification technology. The Pt or Au modified porous PdFe intermetallic compound prepared by the invention has higher activity and stability when being used as a cathode oxygen reduction reaction catalyst and an anode hydrogen oxidation reaction catalyst of a fuel cell.

Description

Pt or Au modified porous PdFe intermetallic compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemistry, relates to a Pt or Au modified porous PdFe intermetallic compound, and a preparation method and application thereof, and particularly relates to an electrocatalyst applied to cathode oxygen reduction and anode hydrogen oxidation reactions of a fuel cell.
Background
With the establishment of a schedule for prohibition of selling fuel vehicles in various countries, Proton Exchange Membrane Fuel Cells (PEMFCs), which are represented by hydrogen-oxygen fuel cells, are entering a high-speed development period. The oxyhydrogen fuel cell device has the general advantages of the fuel cell, such as high power generation efficiency and less environmental pollution, and also has the advantages of quick start at room temperature, less electrolyte loss, high specific power, long service life and the like. However, the PEMFC key material aspect still remains to be further broken through, while the cost needs to be greatly reduced. In particular, the Pt catalyst used in the battery is expensive and easily poisoned and deactivated, which severely limits the commercialization process. It is currently a recognized challenge to explore non-Pt based or low Pt based catalysts that are effective in reducing electrode polarization, thereby improving the output voltage and performance of the cell. An ideal PEMFC catalyst should have the following characteristics: the catalyst has high catalytic activity, more catalytic active sites and better anti-poisoning capacity; secondly, the stability is good, the corrosion resistance and the oxidation resistance are good, and a certain operation period can be met; and thirdly, the cost is low, the dependence of the catalyst on noble metal is reduced as much as possible, and the preparation process is improved. In the long run, reducing the amount of Pt and developing other catalysts with richer reserves is critical to reducing PEMFC cost.
It is well known that Pd is in the same family as Pt and has a very similar electronic structure, so Pd is a catalyst with great potential to replace Pt. In recent years, researchers have been working on economically, rapidly, and mass-producing highly dispersed Pd nanocatalysts to improve the utilization of Pd and reduce the cost of the catalyst. Conventional commercial Pd/C and reported Pd-based catalysts still need to be further improved in activity, particularly stability, and the exploration of novel Pd-based catalysts for fuel cell reactions is imperative.
Disclosure of Invention
The invention solves the technical problems of low catalytic activity and poor cycle stability of the fuel cell in the prior art. The invention aims to provide a Pt or Au modified porous PdFe intermetallic compound and a preparation method and application thereof. The PdFe intermetallic compound uniformly dispersed on the carbon carrier is prepared by high-temperature heat treatment of the acetate precursor, and the Pt or Au modified porous PdFe intermetallic compound is obtained by etching and surface modification technologies.
According to the first aspect of the invention, a Pt or Au modified nano-scale porous PdFe intermetallic compound is provided, the intermetallic compound is a nanoparticle, the inner core of the nanoparticle is an ordered PdFe intermetallic compound, the surface of the nanoparticle is a porous structure with uniformly distributed Pd atoms, and the surface of the porous structure is modified with Pt or Au.
Preferably, the nanoparticles have a diameter of 10nm to 20 nm.
According to another aspect of the present invention, there is provided a method for preparing a Pt or Au modified nanoporous PdFe intermetallic compound, comprising the steps of:
(1) preparing a precursor of the carbon carrier adsorption acetate: adding palladium acetate, ferric salt and a carbon carrier into acetic acid, fully and uniformly mixing, evaporating a solvent to enable the palladium acetate and the ferric salt to be uniformly adsorbed on the surface of the carbon carrier, and drying to obtain a precursor of the palladium acetate and the ferric salt uniformly adsorbed on the carbon carrier; the ferric salt is ferrous acetate or ferric acetate;
(2) preparing a PdFe intermetallic compound: roasting the precursor obtained in the step (1) in a protective atmosphere at the roasting temperature of 600-700 ℃ to thermally decompose acetate in the precursor to obtain a PdFe intermetallic compound;
(3) preparing a PdFe intermetallic compound with a surface porous structure: adding the PdFe intermetallic compound obtained in the step (2) into a mixed solvent of organic alcohol and hydrochloric acid aqueous solution for soaking, wherein the final concentration of hydrochloric acid is 0.2-0.5 mol/L, and etching Fe atoms on the surface of the PdFe intermetallic compound to form a PdFe intermetallic compound with porous surface;
(4) preparing a Pt or Au modified PdFe intermetallic compound with a surface porous structure: and (4) adding the PdFe intermetallic compound with the porous surface obtained in the step (3) into chloroplatinic acid aqueous solution, chloroauric acid aqueous solution or platinum salt aqueous solution for soaking, so that Pt or Au is modified on the surface of the PdFe intermetallic compound with the porous structure, and obtaining the PdFe intermetallic compound with the porous structure modified by Pt or Au.
Preferably, in the step (1), the mass ratio of the Pd atoms to the Fe atoms in the precursor is (1-1.2):1, and the mass fraction of the Pd atoms in the precursor is 5-50%;
preferably, the mass fraction of Pd atoms in the precursor is 10% -30%.
Preferably, the roasting time in the step (2) is 0.5-4 h;
preferably, the roasting time in the step (2) is 30min-180 min.
Preferably, the soaking time in the step (3) is 2h-4h, the volume ratio of the organic alcohol to the hydrochloric acid aqueous solution in the mixed solvent is (1:2) -5, and the mixed solution is an oxygen-removing solution;
preferably, the organic alcohol is ethanol.
Preferably, the soaking time in the step (4) is 30min-60min, the concentration of the chloroplatinic acid aqueous solution, the chloroauric acid aqueous solution or the platinum salt aqueous solution is 0.01mol/L-0.05mol/L, and the platinum salt is potassium chloroplatinate, sodium chloroplatinate or sodium chloroplatinate.
According to another aspect of the invention, the application of the Pt or Au modified nano-scale porous PdFe intermetallic compound in a fuel cell electrode reaction catalyst is provided.
Preferably, the electrode reaction is a cathodic oxygen reduction reaction or an anodic hydrogen oxidation reaction.
Preferably, the fuel cell is a proton exchange membrane fuel cell;
preferably, the proton exchange membrane fuel cell is a hydrogen-oxygen fuel cell.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the invention discloses a preparation method of a novel ordered PdFe intermetallic compound, which further improves the catalytic activity and the cycle stability of the compound by etching and Pt or Au modification technology. The prepared catalyst has the following advantages: uniform particle size distribution; the porous structure can provide more catalytic sites, increase the contact area with reactants and simultaneously facilitate the transmission and diffusion of electrolyte; and thirdly, a small amount of Pt or Au modification can improve the corrosion resistance of the catalyst, inhibit the dissolution loss of Pd atoms and prevent the aggregation of particles in the catalytic process, thereby having better electrochemical stability. Meanwhile, the method has the advantages of simple required equipment, simple and convenient operation and low cost, and is suitable for batch production. The prepared catalyst is applied to the cathode and anode reaction of the fuel cell, the catalytic performance of the catalyst accords with expectation, and the catalyst has the potential of large-scale production of popularization.
(2) In the method, Pd and Fe acetate are used as metal sources, carbon is used as a carrier, and the PdFe intermetallic compound is prepared in one step by a thermal decomposition method. The product has uniform size and regular shape, wherein the particle diameter of the PdFe nano particles is about 10nm and the PdFe nano particles are uniformly loaded on a carrier. After the catalyst is modified by adopting a proper pore-forming and Pt or Au modification technology, the Pt or Au modified PdFe intermetallic compound has higher cathode oxygen reduction electrocatalytic activity and stability, and is also suitable for an anode hydrogen oxidation reaction catalyst.
(3) The invention relates to a preparation method of a novel hydrogen-oxygen fuel cell cathode-anode electrocatalyst. The ordered PdFe intermetallic compound is prepared by a high-temperature thermal decomposition method which is simple and convenient and can realize large-scale production, and the porous PdFe intermetallic compound modified by Pt or Au is obtained by further surface treatment. The selected acetate precursor is cheap and easy to obtain, and compared with the traditional preparation method for preparing the Pd/C or Pt/C catalyst, the method is simpler and easier in process, low in cost and simple in equipment, and can realize batch production; the obtained product has regular appearance and uniform particle size. The porous structure catalyst modified by Pt or Au on the surface has the advantages of more active sites, high electrocatalytic activity, improved stability and the like. Compared with a commercial 20% Pt/C catalyst purchased from Johnson Matthey company, the prepared Pt or Au modified porous PdFe intermetallic compound catalyst has more excellent oxygen reduction and hydrogen oxidation performances, is a fuel cell catalyst with extremely high potential, and has wide application prospect in future hydrogen energy fuel cell automobiles.
(4) In the etching step, organic alcohol, especially ethanol and hydrochloric acid aqueous solution are selected, the final concentration of the hydrochloric acid is 0.2-0.5 mol/L, the alcohol solution can well disperse the carbon-supported intermetallic compound, and the hydrochloric acid solution can etch iron on the surface of the intermetallic compound to form a porous structure.
(5) In the step of thermal decomposition, the temperature is selected to be 600-700 ℃, and the low temperature is not beneficial to forming intermetallic compounds; too high a temperature causes aggregation of catalyst particles, resulting in a decrease in catalytic activity.
(6) According to the invention, acetate is selected to prepare the precursor, and acetate generated in the thermal decomposition process of the acetate can serve as a reducing agent, so that the use of reducing atmosphere is avoided, the process is simplified, the cost is saved, and the segregation and aggregation of Pd in the reducing atmosphere are avoided.
(7) In the etching process, the solution is preferably subjected to oxygen removal treatment, and oxygen removal can ensure that the Pt or Au modification process is carried out more quickly, the modification is more uniform, and the effect is better.
Drawings
Fig. 1 is an XRD pattern of Pt-modified porous PdFe intermetallic compound prepared according to the method example 1 of the present invention.
Fig. 2 is a STEM map of a Pt-modified porous PdFe intermetallic compound prepared according to example 2 of the method of the present invention, fig. 3 is an enlarged view within a box of fig. 2, fig. 4, 5 and 6 are Pd, Fe and Pt element distribution diagrams, respectively, and fig. 7 is an overlay of fig. 4, 5 and 6.
FIG. 8 is a polarization curve of oxygen reduction reaction of Pt modified porous PdFe intermetallic compound prepared according to embodiment 3 of the method of the present invention.
FIG. 9 shows the hydrogen oxidation polarization curve of the Pt modified porous PdFe intermetallic compound prepared according to the method of example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A preparation method of a Pt modified porous PdFe intermetallic compound electrocatalyst comprises the following steps:
(1) preparation of PdFe intermetallic compound: weighing 70mg of carbon carrier, adding the carbon carrier into 4mL of acetic acid solution, adding two reactants of 42.65mg of palladium acetate and 33.06mg of ferrous acetate after sufficient and uniform ultrasonic dispersion, evaporating the solvent after uniform ultrasonic dispersion again, and drying to obtain a precursor sample, wherein the mass fraction of Pd in the precursor (containing the carbon carrier) is 20%; and (3) carrying out thermal decomposition treatment on the prepared black powder in argon flow by programmed temperature rise to 700 ℃, keeping for 120min, and cooling to room temperature to obtain the black powder.
(2) Porous PdFe intermetallic compound: adding a certain amount of the prepared black powder into a mixed solvent of ethanol and a hydrochloric acid aqueous solution (1:1, volume ratio), and soaking for 2h to etch Fe atoms on the surface of the PdFe intermetallic compound and enrich Pd; centrifuging and drying to obtain a PdFe intermetallic compound with a porous structure;
(3) pt-modified porous PdFe intermetallic compound: and (3) adding the product obtained in the step (2) into a chloroplatinic acid solution of 0.05mol/L (nitrogen is removed by oxygen in 30min at the early stage), soaking for 30min, then centrifugally washing, and drying to obtain a black final product.
Example 2
A preparation method of a Pt modified porous PdFe intermetallic compound electrocatalyst comprises the following steps:
(1) 70mg of carbon carrier, 42.65mg of Pd (Ac)2And 33.06mg Fe (Ac)2And sequentially adding the solution into 4mL of acetic acid solution, fully and uniformly performing ultrasonic treatment, evaporating the solvent, and drying to obtain a precursor sample, wherein the mass fraction of Pd in the precursor (containing a carbon carrier) is 20%. And (3) carrying out thermal decomposition on the prepared black powder in nitrogen gas flow by temperature programming to 650 ℃, keeping for 120min, and cooling to room temperature to obtain the PdFe intermetallic compound.
(2) Adding a certain amount of black powder prepared in the step (1) into a mixed solvent of ethanol and 0.5mol/L hydrochloric acid water solution (1:1, volume ratio), and soaking for 2 hours to etch Fe atoms on the surface of the PdFe intermetallic compound and enrich Pd; and (4) centrifugally drying to obtain the PdFe intermetallic compound with the porous structure.
(3) And (3) adding the product obtained in the step (2) into a 0.05M chloroplatinic acid solution (30 min nitrogen deoxygenation is carried out in the early stage), soaking for 35min, then carrying out centrifugal washing, and drying to obtain a black final product.
Example 3
A preparation method of a Pt modified porous PdFe intermetallic compound electrocatalyst comprises the following steps:
(1) weighing 85mg Pd (Ac)2And 66mg Fe (Ac)2Adding into 8mL acetic acid solution, adding 140mg carbon black after sufficient ultrasonic homogenization, evaporating to dissolve after ultrasonic homogenizationDrying to obtain a precursor sample, wherein the mass fraction of Pd in the precursor (containing the carbon carrier) is 20%. And (3) carrying out thermal decomposition on the prepared black powder in nitrogen gas flow by temperature programming to 650 ℃, keeping for 120min, and cooling to room temperature to obtain the PdFe intermetallic compound.
(2) Porous PdFe intermetallic compound: adding a certain amount of black powder prepared in the step (1) into a mixed solvent of 0.5M hydrochloric acid aqueous solution and ethylene glycol, and soaking for 1h to etch Fe atoms on the surface of the PdFe intermetallic compound and enrich Pd; centrifugally drying to obtain a PdFe intermetallic compound with a porous structure;
(3) pt-modified porous PdFe intermetallic compound: and (3) adding the product obtained in the step (2) into a 0.1mol/L chloroplatinic acid solution (nitrogen is removed in the early stage for 30-60 min), soaking for 30min, then centrifugally washing, and drying to obtain a black final product.
Example 4
A preparation method of a Pt modified porous PdFe intermetallic compound electrocatalyst comprises the following steps:
(1) mixing and adsorbing a precursor sample: weighing 140mg of carbon black, 95mg of Pd (Ac)2And 80mgFe (Ac)2Sequentially adding the mixture into 8mL of acetic acid solution, uniformly mixing, evaporating the solvent to dryness, and drying to obtain a precursor sample, wherein Pd accounts for 21% of the mass fraction of the precursor (containing carbon carriers);
(2) preparing a PdFe intermetallic compound: the prepared black powder is decomposed by temperature programmed to 600-700 ℃ in argon-hydrogen gas flow, and cooled to room temperature after being kept for 60min, so as to obtain an intermetallic compound;
(3) porous PdFe intermetallic compound: adding a certain amount of black powder prepared in the step (2) into a mixed solvent of 0.5M HCl aqueous solution and ethanol, and continuously stirring for 30min to etch Fe atoms on the surface of the PdFe intermetallic compound and enrich Pd; centrifugally drying to obtain a PdFe intermetallic compound with a porous structure;
(4) pt-modified porous PdFe intermetallic compound: and (3) adding 50mg of the product obtained in the step (3) into a 0.1 potassium chloroplatinate solution (30 min for introducing nitrogen to remove oxygen in the early stage), soaking for 40min, centrifuging, washing, and drying to obtain a black final product.
Example 5
A preparation method of a Pt modified porous PdFe intermetallic compound electrocatalyst comprises the following steps:
(1) mixing and adsorbing a precursor sample: weighing 140mg of carbon black, 85mg of Pd (Ac)2And 70mgFe (OAc)3Adding the mixture into 10mL of acetic acid solution, uniformly mixing, and evaporating the solvent to obtain a precursor sample, wherein the mass fraction of Pd in the precursor (containing a carbon carrier) is 18%;
(2) preparing a PdFe intermetallic compound: the prepared black powder is heated to 600-700 ℃ in argon-hydrogen flow by a program and is kept for 100min, and then is cooled to room temperature, so that the PdFe intermetallic compound can be obtained;
(3) preparing a porous PdFe intermetallic compound: adding a certain amount of black powder prepared in the step (2) into a mixed solvent of 0.5M HCl aqueous solution and ethanol, and continuously stirring for 30min to etch Fe atoms on the surface of the PdFe intermetallic compound and enrich Pd; centrifugally drying to obtain a PdFe intermetallic compound with a porous structure;
(4) pt-modified porous PdFe intermetallic compound: and (3) adding 50mg of the product obtained in the step (3) into 0.1mol/L potassium chloroplatinate solution (30 min at the early stage for introducing nitrogen to remove oxygen), soaking for 40min, centrifuging, washing, and drying to obtain a black final product.
Example 6
A preparation method of an Au modified porous PdFe intermetallic compound electrocatalyst comprises the following steps:
(1) mixing and adsorbing a precursor sample: weighing 140mg of carbon black, 85mg of Pd (Ac)2And 70mgFe (Ac)3Adding the mixture into 10mL of acetic acid solution, uniformly mixing, and evaporating the solvent to obtain a precursor sample, wherein the mass fraction of Pd in the precursor is 18%;
(2) preparing a PdFe intermetallic compound: the prepared black powder is heated to 600-700 ℃ in argon-hydrogen flow by a program and is kept for 60min, and then is cooled to room temperature, so that the PdFe intermetallic compound can be obtained;
(3) preparing a porous PdFe intermetallic compound: adding a certain amount of black powder prepared in the step (2) into a mixed solvent of 0.5M HCl aqueous solution and ethanol, and continuously stirring for 30min to etch Fe atoms on the surface of the PdFe intermetallic compound and enrich Pd; centrifugally drying to obtain a PdFe intermetallic compound with a porous structure;
(4) au modified porous PdFe intermetallic compound: and (3) adding 50mg of the product obtained in the step (3) into a 0.2mol/L chloroauric acid solution (30 min at the early stage for introducing nitrogen to remove oxygen), soaking for 40min, then centrifugally washing, and drying to obtain the black Au-modified porous PdFe intermetallic compound.
Results and analysis:
characterization analysis was performed on the Pt-modified porous PdFe intermetallic compound prepared in example 1 and example 2 using XRD and STEM, respectively. Fig. 1 is an XRD pattern of the Pt-modified porous PdFe intermetallic compound prepared according to method example 1 of the present invention. Fig. 2 is a STEM map of a Pt-modified porous PdFe intermetallic compound prepared according to example 2 of the method of the present invention, fig. 3 is an enlarged view within a box of fig. 2, fig. 4, 5 and 6 are Pd, Fe and Pt element distribution diagrams, respectively, and fig. 7 is an overlay of fig. 4, 5 and 6. FIG. 8 is a polarization curve of oxygen reduction reaction of Pt modified porous PdFe intermetallic compound prepared according to embodiment 3 of the method of the present invention. FIG. 9 shows the hydrogen oxidation polarization curve of the Pt modified porous PdFe intermetallic compound prepared according to the method of example 4 of the present invention. From the XRD pattern (fig. 1), it can be seen that the Pt-modified porous PdFe intermetallic compound can be successfully prepared, consistent with the standard card of ordered structure. It can be seen from STEM (FIGS. 2 and 3) that the prepared Pt modified porous PdFe intermetallic compound has a particle size of about 10-20nm and is uniformly dispersed on the carbon carrier. The porous structure is relatively uniform and obvious; as can be seen from fig. 4, 5, 6 and 7, the Pd and Fe elements are distributed more uniformly, but the Pt signal is weaker, confirming that the content is smaller. Finally, the prepared Pt modified porous PdFe intermetallic compound electrocatalyst is applied to the ORR catalytic reaction by taking commercial 20% Pd/C and 20% Pt/C as reference catalysts, and the half-wave potential of the prepared catalyst is shifted by 30mV in comparison with the commercial Pt, and meanwhile, the mass activity reaches 148 mAmp-1Far exceeding 45.73mAmg of commercial Pt catalyst-1(FIG. 8). At the same time, the HOR pole of the prepared catalystThe chemical curve shows a better activity increase by about 3mV negative shift compared to the commercial Pt (fig. 9). The catalyst prepared by the invention can show performance exceeding that of a Pt/C catalyst when being applied to a hydrogen-oxygen fuel cell, and is expected to become a substitute of Pt.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (12)

1. A preparation method of a Pt or Au modified nano-scale porous PdFe intermetallic compound is characterized in that the intermetallic compound is a nano-particle, the inner core of the nano-particle is an ordered PdFe intermetallic compound, the surface of the nano-particle is a porous structure with uniformly distributed Pd atoms, the surface of the porous structure is modified with Pt or Au, and the diameter of the nano-particle is 10nm-20 nm;
the preparation method comprises the following steps:
(1) preparing a precursor of the carbon carrier adsorption acetate: adding palladium acetate, ferric salt and a carbon carrier into acetic acid, fully and uniformly mixing, evaporating a solvent to enable the palladium acetate and the ferric salt to be uniformly adsorbed on the surface of the carbon carrier, and drying to obtain a precursor of the palladium acetate and the ferric salt uniformly adsorbed on the carbon carrier; the ferric salt is ferrous acetate or ferric acetate;
(2) preparing a PdFe intermetallic compound: roasting the precursor obtained in the step (1) in a protective atmosphere at the roasting temperature of 600-700 ℃ to thermally decompose acetate in the precursor to obtain a PdFe intermetallic compound;
(3) preparing a PdFe intermetallic compound with a surface porous structure: adding the PdFe intermetallic compound obtained in the step (2) into a mixed solvent of organic alcohol and hydrochloric acid aqueous solution for soaking, wherein the final concentration of hydrochloric acid is 0.2-0.5 mol/L, and etching Fe atoms on the surface of the PdFe intermetallic compound to form a PdFe intermetallic compound with porous surface;
(4) preparing a Pt or Au modified PdFe intermetallic compound with a surface porous structure: and (4) adding the PdFe intermetallic compound with the porous surface obtained in the step (3) into chloroplatinic acid aqueous solution, chloroauric acid aqueous solution or platinum salt aqueous solution for soaking, so that Pt or Au is modified on the surface of the PdFe intermetallic compound with the porous structure, and obtaining the PdFe intermetallic compound with the porous structure modified by Pt or Au.
2. The method for preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound as claimed in claim 1, wherein the ratio of the amount of Pd atoms to Fe atoms in the precursor in step (1) is (1-1.2):1, and the mass fraction of Pd atoms in the precursor is 5% -50%.
3. The method for preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound as claimed in claim 2, wherein the mass fraction of Pd atoms in the precursor is 10% -30%.
4. The method for preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound as claimed in claim 1, wherein the time for the calcination in the step (2) is 0.5h-4 h.
5. The method for preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound as claimed in claim 4, wherein the time for the calcination in the step (2) is 30min-180 min.
6. The method for preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound as claimed in claim 1, wherein the soaking time in the step (3) is 2h-4h, the volume ratio of the organic alcohol to the hydrochloric acid aqueous solution in the mixed solvent is (1:2) -5, and the mixed solvent is an oxygen-removed solution.
7. The method for preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound according to claim 6, wherein the organic alcohol is ethanol.
8. The method for preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound as claimed in claim 1, wherein the soaking time in the step (4) is 30min-60min, the concentration of the chloroplatinic acid aqueous solution, the chloroauric acid aqueous solution or the platinum salt aqueous solution is 0.01mol/L-0.05mol/L, and the platinum salt is potassium chloroplatinate, sodium chloroplatinate or sodium chloroplatinate.
9. The use of the compound prepared by the method of preparing the Pt or Au modified nano-scale porous PdFe intermetallic compound as claimed in claim 1 in the fuel cell electrode reaction catalyst.
10. Use according to claim 9, wherein the electrode reaction is a cathodic oxygen reduction reaction or an anodic hydrogen oxidation reaction.
11. The use according to claim 10, wherein the fuel cell is a proton exchange membrane fuel cell.
12. The use according to claim 11, wherein the proton exchange membrane fuel cell is a hydrogen-oxygen fuel cell.
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CN101572316B (en) * 2009-06-06 2011-09-07 西北师范大学 Modified catalyst for low-temperature fuel cell and preparation method thereof
CN102166524B (en) * 2011-03-04 2012-10-24 南京师范大学 Method for preparing high-alloying carbon-supported PdFe nanocatalyst by in-situ reduction method
CN103638925B (en) * 2013-11-15 2015-08-26 华南理工大学 A kind of fuel cell catalyst with core-casing structure and pulse electrodeposition preparation method thereof
CN103628102A (en) * 2013-12-09 2014-03-12 深圳市嘉达高科产业发展有限公司 Electroplating solution, Pt-Ru catalyst membrane as well as preparation method thereof and membrane fuel cell
CN105648478A (en) * 2016-01-13 2016-06-08 大连理工大学 Preparation method of magnetic nano porous Fe-Pt alloy with electro-oxidation catalytic performance
CN108767277B (en) * 2018-05-25 2020-10-30 辽宁科技大学 Fe-Pd-based nano-porous material and preparation method thereof
CN109065895A (en) * 2018-07-26 2018-12-21 北京化工大学常州先进材料研究院 The preparation of iron cobalt codope carbon nitrogen core-shell particles material and its application in terms of electro-catalysis
CN109148905A (en) * 2018-09-30 2019-01-04 北京海得利兹新技术有限公司 A kind of polymer dielectric film fuel cell high activity elctro-catalyst and preparation method thereof
CN109694965B (en) * 2018-12-27 2020-12-08 北京工业大学 Copper-based surface porous structure and manufacturing method thereof

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