CN113206264A - Platinum-based intermetallic nanocrystalline with ordered structure and medium and low temperature preparation and application thereof - Google Patents
Platinum-based intermetallic nanocrystalline with ordered structure and medium and low temperature preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a platinum-based intermetallic nanocrystalline with an ordered structure, and medium-low temperature preparation and application thereof, belonging to the field of cathode materials of proton exchange membrane fuel cells. Dispersing a salt formed by platinum salt, transition metal salt and low-melting-point metal into an organic amine solution, and reducing the metal salt in the mixed solution to obtain disordered ternary alloy nanocrystals; loading the obtained nanocrystalline on carbon, and carrying out medium-low temperature annealing treatment on the ternary alloy to obtain the platinum-based intermetallic nanocrystalline oxygen reduction catalyst. The preparation method provided by the invention is simple in process, can reduce the disordered-ordered phase transition temperature of the platinum-transition metal nanocrystalline catalyst, reduce energy consumption, save energy and reduce emission by introducing low-melting-point metal, is easy for industrial batch production, and the obtained platinum-based intermetallic nanocrystalline oxygen reduction catalyst has good activity and durability, and can be applied to proton exchange membrane fuel cells.
Description
Technical Field
The invention belongs to the field of cathode materials of proton exchange membrane fuel cells, and particularly relates to a platinum-based intermetallic nanocrystalline with an ordered structure, as well as medium-low temperature preparation and application thereof, in particular to a platinum-based intermetallic nanocrystalline oxygen reduction catalyst and a preparation method thereof, and particularly relates to a preparation method for reducing the phase transition temperature of the platinum-based intermetallic nanocrystalline, a platinum-based intermetallic nanocrystalline oxygen reduction catalyst for accelerating the cathode oxygen reduction reaction rate of a fuel cell, and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) can convert chemical energy stored in Fuel/oxygen into electrical energy through an electrochemical process, and have the advantages of high conversion efficiency, high specific power, and the like, and meanwhile, the product is nontoxic and harmless water, and is an environment-friendly energy source.
The bottleneck of current fuel cell applications is its high cost, the oxygen reduction reaction rate of the PEMFC cathode is much slower than that of the anode hydrogen oxidation reaction, and noble metal platinum is required as a catalyst to accelerate the oxygen reduction reaction rate. In order to improve the catalyst activity, in the current research, researchers generally alloy platinum with transition metals to improve the oxygen reduction catalytic activity of platinum-based catalysts, but the stability thereof still has problems: that is, under high temperature, high voltage and acidic conditions, the transition metal is easily dissolved, resulting in a decrease in the activity of the catalyst.
Recent studies show that ordered platinum-based PtM catalysts (also called intermetallic compounds) have stronger corrosion resistance to transition metals in the ordered platinum-based intermetallic catalysts due to stronger interaction between platinum and the 5d-3d orbital electrons between transition metal atoms. But the main problems at present are that: the catalyst can complete the phase change from disorder to order after heat treatment, and the formed ordered alloy, namely intermetallic compound, can greatly improve the structural stability and the electrochemical stability. The invention patent (CN201910866474.7) prepares a small-size highly-dispersed intermetallic compound catalyst material by impregnating an MOF-derived carbon material with a solution containing a noble metal precursor and a non-noble metal precursor, freeze-drying, and then treating at high temperature (650-850 ℃) in an environment containing a reducing atmosphere. The invention patent (CN202010005386.0) discloses a preparation method of a non-metal stable supported platinum-based intermetallic compound, which is prepared by secondary heat treatment (550-1000 ℃). The invention patent (CN201911049649.1) carries out annealing treatment (550-700 ℃) on a platinum and metal oxide compound to obtain the platinum-based intermetallic nanocrystalline oxygen reduction catalyst.
The high-temperature ordering treatment can cause the agglomeration of catalyst nano particles, the reduction of the electrochemical specific surface and the lower utilization rate of platinum atoms, thereby causing the reduction of the activity of the catalyst; on the other hand, high-temperature treatment causes large energy consumption of a technical route, and is not beneficial to industrial popularization. Therefore, in the heat treatment process of forming the ordered intermetallic compound, a method for preparing the platinum-based intermetallic nanocrystalline catalyst at medium and low temperature (less than 500 ℃) is found, so that the method has the advantages of energy conservation, emission reduction and cost saving, and has important significance.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides a method for preparing a platinum-based intermetallic nanocrystalline with an ordered structure at a medium and low temperature, which aims to introduce a third low-melting-point metal into a binary platinum-based alloy, weaken the bond energy in the binary alloy, reduce the activation energy of phase change, reduce the disordered-ordered phase change temperature of platinum-transition metal (PtM alloy catalyst) by about 200 ℃ on average, realize the medium and low temperature (less than 500 ℃) phase change of the nanocrystalline, finally obtain the platinum-based intermetallic nanocrystalline oxygen reduction catalyst with uniform size and smaller particle size, have good activity and durability, simple synthesis process, energy conservation and emission reduction, reduce cost and facilitate batch production, thereby solving the problems that the high-temperature ordered treatment can cause the agglomeration of catalyst nanoparticles, the reduction of the electrochemical specific surface and the lower utilization rate of platinum atoms, thereby causing a technical problem of a decrease in catalyst activity.
According to a first aspect of the present invention, there is provided a method for preparing a structurally ordered platinum-based intermetallic nanocrystal, comprising the steps of:
(1) dissolving a salt formed by platinum salt, transition metal salt and low-melting-point metal in organic amine to form a mixed dispersion liquid, wherein the melting point of the low-melting-point metal is below 250 ℃;
(2) heating the mixed dispersion liquid obtained in the step (1) in a protective atmosphere to reduce a platinum salt, a transition metal salt and a salt formed by a low-melting metal by using an amino group, so as to obtain disordered ternary alloy nanoparticles;
(3) dispersing carbon powder into an organic solvent to form a dispersion liquid, and then dropwise adding the dispersion liquid into the disordered ternary alloy nanoparticles obtained in the step (2) to obtain carbon-supported nanoparticles;
(4) and (3) under a reducing atmosphere, carrying out heating annealing treatment on the carbon-supported nanoparticles obtained in the step (3) to rearrange atoms in the disordered ternary alloy nanoparticles, thereby obtaining the structurally-ordered platinum-based intermetallic nanocrystals.
Preferably, the heating temperature in the step (4) is 350-500 ℃, and the heating time in the step (4) is 1-5 h.
Preferably, the low-melting-point metal is tin, gallium or indium, and the salt formed by the low-melting-point metal is at least one of acetate of the low-melting-point metal, acetylacetone salt of the low-melting-point metal and dibutyl diacetone salt of the low-melting-point metal; the platinum salt is at least one of chloroplatinic acid and platinum acetylacetonate; the organic amine is at least one of oleylamine, octadecylamine and hexadecylamine; the transition metal salt is at least one of acetate of transition metal, chloride of transition metal and acetylacetone salt of transition metal;
preferably, the acetate of the transition metal is at least one of iron acetate, nickel acetate and zinc acetate; the chloride of the transition metal is at least one of ferric chloride, nickel chloride and zinc chloride; the acetylacetone salt of the transition metal is at least one of iron acetylacetonate, nickel acetylacetonate and zinc acetylacetonate.
Preferably, the concentration of the platinum salt in the mixed dispersion liquid in the step (1) is 0.01mol/L to 0.05 mol/L.
Preferably, the ratio of the amounts of the platinum salt, the transition metal salt and the low melting point metal salt in step (1) is 50: (35-45): (5-15).
Preferably, the heating temperature of the step (2) is 250-320 ℃, and the time is 0.5-2 h; the heating rate is 5-10 deg.C/min.
Preferably, the mass ratio of the carbon powder to the disordered ternary alloy nanoparticles in the step (3) is (8-9): (1-2).
According to another aspect of the invention, the structurally ordered platinum-based intermetallic nanocrystals prepared by any of the methods are provided.
Preferably, the diameter of the nanocrystal is 3nm-6 nm; the ratio of the amount of platinum atoms, transition metal atoms and low-melting metal atoms in the nanocrystalline is 50: (35-45): (5-15).
According to another aspect of the invention, the application of the structurally-ordered platinum-based intermetallic nanocrystalline for the cathode oxygen reduction catalyst of the proton exchange membrane fuel cell is provided.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the invention designs a method for preparing platinum-based intermetallic nanocrystals at medium and low temperature from the aspects of thermodynamics and kinetics. The principle is that a third low-melting-point metal M' is introduced into the binary platinum-based PtM alloy, so that the bond energy in the binary alloy can be weakened, and the activation energy of phase change can be reduced, thereby reducing the phase change temperature and realizing the medium-low temperature (less than 500 ℃) phase change of the nanocrystalline. The method is simple to operate, can prepare the platinum-based intermetallic nanocrystalline oxygen reduction catalyst with controllable size and smaller particle size, and is very important for large-scale production of the catalyst and promotion of the application of fuel cell technology.
(2) The invention provides a method for preparing a platinum-based intermetallic nanocrystalline catalyst by reducing the phase transition temperature of nanocrystals and realizing medium-low temperature phase transition, which can averagely reduce the phase transition temperature of platinum-transition metal (PtM alloy catalyst) to 200 ℃, reduce the diffusion and phase transition activation energy through the controllable doping of low-melting-point metal, realize the medium-low temperature phase transition of nanocrystals, save energy, reduce emission, reduce cost and is easy for industrial popularization.
(3) The method for preparing the platinum-based intermetallic nanocrystalline at the medium and low temperature, disclosed by the invention, has the advantages that the agglomeration degree of the nanocrystalline is remarkably reduced by greatly reducing the heat treatment temperature, the prepared platinum-based intermetallic nanocrystalline has smaller particle size, the particle size is 3-6nm, the size is uniform, compared with the existing ordered nanoparticles, the size is smaller, the electrochemical active area is increased, the utilization rate of platinum atoms can be greatly increased, and the activity of a catalyst is improved. In addition, compared with small-sized disordered nanocrystals, the ordered structure nanocrystals prepared by the invention can realize higher structural stability and electrochemical stability.
(4) In a high-temperature environment, formed intermetallic compound nano particles are easy to agglomerate and grow, and the agglomeration and growth of ordered intermetallic compound particles seriously influence the activity of the nano material.
(5) The prepared platinum-based intermetallic nanocrystalline oxygen reduction catalyst has excellent oxygen reduction catalytic performance, compared with a commercial platinum-carbon catalyst, the oxygen reduction half-wave potential of the platinum-based intermetallic nanocrystalline oxygen reduction catalyst is improved by 70mV, and the performance is only attenuated by 6mV after 50000 cycles.
Drawings
Fig. 1 is a flow chart of a preparation process of a platinum-based intermetallic nanocrystalline oxygen reduction catalyst according to an embodiment of the present invention.
FIG. 2 is a transmission electron microscope image of the Pt-Zn-Sn intermetallic nanocrystalline oxygen reduction catalyst prepared in example 1 of the present invention.
Fig. 3 is an XRD pattern of the platinum zinc tin intermetallic nanocrystalline oxygen reduction catalyst prepared in example 1 of the present invention.
Fig. 4 is a transmission electron microscope image of the platinum nickel tin intermetallic nanocrystalline oxygen reduction catalyst prepared in example 2 of the present invention.
Fig. 5 is an XRD pattern of the platinum-nickel-tin intermetallic nanocrystalline oxygen reduction catalyst prepared in example 2 of the present invention.
Fig. 6 is a graph of oxygen reduction performance of a platinum nickel tin intermetallic nanocrystalline oxygen reduction catalyst prepared in example 2 of the present invention compared to a commercial platinum carbon catalyst.
Fig. 7 is a graph of the oxygen reduction stability of the platinum nickel tin intermetallic nanocrystalline oxygen reduction catalyst prepared in example 2 of the present invention.
Fig. 8 is a transmission electron microscope image of the platinum iron tin intermetallic nanocrystalline oxygen reduction catalyst prepared in example 3 of the present invention.
Fig. 9 is an XRD pattern of the platinum-iron-tin intermetallic nanocrystalline oxygen reduction catalyst prepared in example 3 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.
The method for reducing the phase transition temperature of the platinum-based intermetallic nanocrystalline provided by the embodiment of the invention has the preparation flow shown in figure 1, and comprises the following specific preparation steps:
s1: dissolving a salt formed by platinum salt, transition metal salt and low-melting point metal into an organic amine solution to obtain a solution with the platinum salt concentration of 0.01-0.05 mol/L, and heating to 100-130 ℃ under the protection of inert atmosphere to completely dissolve the platinum salt;
s2: slowly heating the solution to 250-320 ℃ at a certain heating rate, reducing the metal salt under the protection of organic amine molecules to obtain disordered ternary alloy nanoparticles with uniform size, centrifuging and washing to obtain ternary alloy nanoparticles, and dispersing the ternary alloy nanoparticles into a hexane solution for later use;
s3: and (3) weighing a certain mass of carbon powder according to the metal loading capacity in a beaker, adding a mixed solution of ethanol and hexane in a volume ratio of 2:1, performing ultrasonic dispersion, and then slowly dropping the ternary alloy nanoparticles obtained in the step S2. After ultrasonic treatment for a period of time, centrifuging, washing and drying to obtain carbon-supported nanoparticles;
s4: and (4) performing medium-low temperature ordered heat treatment on the carbon-supported nanoparticles obtained in the step (S3) in a reducing atmosphere to obtain the platinum-based ordered intermetallic compound with uniform size and smaller particle size.
The following are specific examples:
example 1
S1: according to the molar ratio of 5:4:1, platinum acetylacetonate, zinc acetylacetonate and dibutyl diacetone tin are dissolved in 5mL of oleylamine solution to prepare a solution with the platinum precursor concentration of 0.01 mol/L. Under the protection of argon, the solution is stirred for 20 minutes at 110 ℃, and precursor salt is fully dissolved and mixed.
S2: and then, heating the solution to 320 ℃ at a heating rate of 10 ℃/min, continuing to react for 2 hours, and then centrifugally washing to obtain the disordered platinum-zinc-tin nanoparticles.
S3: weighing a certain mass of carbon powder according to the metal loading capacity of 15%, adding a mixed solution of ethanol and hexane in a volume ratio of 2:1, performing ultrasonic dispersion, and then slowly dropping the disordered ternary platinum-zinc-tin nanoparticles obtained in the step S2. After ultrasonic treatment for a period of time, centrifuging, washing and drying to obtain carbon-supported disordered platinum-zinc-tin ternary nanoparticles;
s4: and placing the obtained carbon-supported disordered platinum-zinc-tin ternary nanoparticles into a tubular furnace, and annealing for 1 hour at 350 ℃ in an argon-hydrogen atmosphere. And cooling to obtain the ordered Pt-Zn-Sn nanoparticles. As shown in FIGS. 2 and 3, which are a transmission electron micrograph and an XRD micrograph of the catalyst, respectively, it can be seen from FIG. 2 that the nanocrystals obtained in this example have a small particle size of 3 nm. As can be seen from fig. 3, the crystal structure of the nanocrystal obtained in this example is well matched with the structure of ordered pt-zn.
Example 2
S1: according to the molar ratio of 50:35:15, platinum acetylacetonate, nickel acetylacetonate and dibutyl diacetone tin are dissolved in 5mL of oleylamine solution to prepare a solution with the platinum precursor concentration of 0.05 mol/L. Under the protection of argon, the solution is stirred for 20 minutes at 100 ℃, and precursor salt is fully dissolved and mixed.
S2: then, heating the solution to 260 ℃ at a heating rate of 5 ℃/min, continuing to react for 1 hour, and then centrifugally washing to obtain disordered platinum-nickel-tin ternary nanoparticles;
s3: weighing a certain mass of carbon powder according to the metal loading capacity of 20%, adding a mixed solution of ethanol and hexane in a volume ratio of 2:1, performing ultrasonic dispersion, and then slowly dropping the disordered ternary platinum-nickel-tin nanoparticles obtained in the step S2. After ultrasonic treatment for a period of time, centrifuging, washing and drying to obtain carbon-supported disordered platinum-nickel-tin ternary nanoparticles;
s4: and placing the obtained carbon-supported disordered platinum-nickel-tin ternary nano particles into a tubular furnace, and annealing for 2 hours at 450 ℃ in an argon-hydrogen atmosphere. And cooling to obtain the ordered platinum-nickel-tin nanoparticles. As shown in FIGS. 4 and 5, which are a transmission electron micrograph and an XRD micrograph of the catalyst, respectively, it can be seen from FIG. 4 that the nanocrystals obtained in this example have a small particle size of 3.5 nm. As can be seen from fig. 5, the crystal structure of the nanocrystal obtained in this example is well matched with the structure of ordered platinum nickel. As can be seen from FIG. 6, the catalyst obtained in this example has a better oxygen reduction activity and an increase in the half-wave potential of 70mV compared to the commercial platinum-carbon catalyst. As can be seen from FIG. 7, the catalyst obtained in this example has good cycle stability, and the performance decays by only 6mV after 50000 cycles of circulation.
Example 3
S1: according to the molar ratio of 50:45:5, platinum acetylacetonate, iron acetate and dibutyl diacetone tin are taken and dissolved in 5mL of oleylamine solution to prepare a solution with the platinum precursor concentration of 0.01 mol/L. Under the protection of argon, the solution is stirred for 20 minutes at 130 ℃, and precursor salt is fully dissolved and mixed.
S2: then, heating the solution to 260 ℃ at a heating rate of 5 ℃/min, continuing to react for 1 hour, and then centrifugally washing to obtain disordered ternary Pt-Fe-Sn nanoparticles;
s3: weighing a certain mass of carbon powder according to the metal loading capacity of 10%, adding a mixed solution of ethanol and hexane in a volume ratio of 2:1, performing ultrasonic dispersion, and then slowly dropping the disordered ternary Pt-Fe-Sn nanoparticles obtained in the step S2. After ultrasonic treatment for a period of time, centrifuging, washing and drying to obtain carbon-supported disordered platinum-iron-tin ternary nanoparticles;
s4: and placing the obtained carbon-supported disordered platinum-iron-tin ternary nanoparticles into a tubular furnace, and annealing for 2 hours at 450 ℃ in an argon-hydrogen atmosphere. And cooling to obtain the ordered Pt-Fe-Sn nanoparticles. As shown in FIGS. 6 and 7, which are a transmission electron micrograph and an XRD micrograph of the catalyst, respectively, it can be seen from FIG. 8 that the nanocrystals obtained in this example have a small particle size of 6 nm. As can be seen from fig. 9, the crystal structure of the nanocrystal obtained in this example is well matched with the structure of ordered platinum iron.
Example 4
S1: according to the molar ratio of 50:35:15, chloroplatinic acid, nickel chloride and indium acetate are dissolved in 5mL hexadecylamine solution to prepare solution with platinum precursor concentration of 0.03 mol/L. Under the protection of argon, the solution is stirred for 20 minutes at 110 ℃, and precursor salt is fully dissolved and mixed.
S2: subsequently, heating the solution to 260 ℃ at a heating rate of 5 ℃/min, continuing to react for 1 hour, and then centrifugally washing to obtain disordered ternary platinum-nickel-indium nanoparticles;
s3: weighing a certain mass of carbon powder according to the metal loading capacity of 15%, adding a mixed solution of ethanol and hexane in a volume ratio of 2:1, performing ultrasonic dispersion, and then slowly dropping the disordered ternary Pt-Fe-Sn nanoparticles obtained in the step S2. After ultrasonic treatment for a period of time, centrifuging, washing and drying to obtain carbon-supported disordered platinum-iron-tin ternary nanoparticles;
s4: and placing the obtained carbon-supported disordered platinum-nickel-indium ternary nano particles into a tubular furnace, and annealing for 2 hours at 500 ℃ in an argon-hydrogen atmosphere. And cooling to obtain the ordered platinum-nickel-indium nanoparticles.
Example 5
S1: according to the molar ratio of 50:35:15, chloroplatinic acid, nickel acetate and gallium acetylacetonate are dissolved in 5mL of octadecylamine solution to prepare a solution with the platinum precursor concentration of 0.025 mol/L. Under the protection of argon, the solution is stirred for 20 minutes at 120 ℃, and precursor salt is fully dissolved and mixed.
S2: then, heating the solution to 280 ℃ at a heating rate of 5 ℃/min, continuing to react for 1 hour, and then centrifugally washing to obtain disordered platinum-nickel-gallium ternary nanoparticles;
s3: weighing a certain mass of carbon powder according to the metal loading capacity of 15%, adding a mixed solution of ethanol and hexane in a volume ratio of 2:1, performing ultrasonic dispersion, and then slowly dropping the disordered ternary Pt-Fe-Sn nanoparticles obtained in the step S2. After ultrasonic treatment for a period of time, centrifuging, washing and drying to obtain carbon-supported disordered platinum-iron-tin ternary nanoparticles;
s4: and placing the obtained carbon-supported disordered platinum-nickel-gallium ternary nano particles into a tube furnace, and annealing for 2 hours at 500 ℃ in an argon-hydrogen atmosphere. And cooling to obtain the ordered platinum nickel gallium nano particles.
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 (10)
1. A method for preparing a platinum-based intermetallic nanocrystal with an ordered structure is characterized by comprising the following steps:
(1) dissolving a salt formed by platinum salt, transition metal salt and low-melting-point metal in organic amine to form a mixed dispersion liquid, wherein the melting point of the low-melting-point metal is below 250 ℃;
(2) heating the mixed dispersion liquid obtained in the step (1) in a protective atmosphere to reduce a platinum salt, a transition metal salt and a salt formed by a low-melting metal by using an amino group, so as to obtain disordered ternary alloy nanoparticles;
(3) dispersing carbon powder into an organic solvent to form a dispersion liquid, and then dropwise adding the dispersion liquid into the disordered ternary alloy nanoparticles obtained in the step (2) to obtain carbon-supported nanoparticles;
(4) and (3) under a reducing atmosphere, carrying out heating annealing treatment on the carbon-supported nanoparticles obtained in the step (3) to rearrange atoms in the disordered ternary alloy nanoparticles, thereby obtaining the structurally-ordered platinum-based intermetallic nanocrystals.
2. The method for preparing a structurally ordered platinum-based intermetallic nanocrystal according to claim 1, characterized in that the temperature of the heating in step (4) is between 350 ℃ and 500 ℃ and the time of the heating in step (4) is between 1h and 5 h.
3. The method for preparing a structurally ordered platinum-based intermetallic nanocrystal according to claim 1 or 2, characterized in that the low melting point metal is tin, gallium or indium, and the salt formed by the low melting point metal is at least one of acetate of the low melting point metal, acetylacetonate of the low melting point metal and dibutyldiacetylacetonato of the low melting point metal; the platinum salt is at least one of chloroplatinic acid and platinum acetylacetonate; the organic amine is at least one of oleylamine, octadecylamine and hexadecylamine; the transition metal salt is at least one of acetate of transition metal, chloride of transition metal and acetylacetone salt of transition metal;
preferably, the acetate of the transition metal is at least one of iron acetate, nickel acetate and zinc acetate; the chloride of the transition metal is at least one of ferric chloride, nickel chloride and zinc chloride; the acetylacetone salt of the transition metal is at least one of iron acetylacetonate, nickel acetylacetonate and zinc acetylacetonate.
4. The method for producing a structurally ordered platinum-based intermetallic nanocrystal according to claim 1 or 2, characterized in that the concentration of the platinum salt in the mixed dispersion in step (1) is 0.01mol/L to 0.05 mol/L.
5. The method for producing a structurally ordered platinum-based intermetallic nanocrystal according to claim 1 or 2, characterized in that the ratio of the amounts of substances of the platinum salt, the salt of the transition metal and the salt of the low-melting metal in step (1) is 50: (35-45): (5-15).
6. The method for preparing a structurally ordered platinum-based intermetallic nanocrystal according to claim 1 or 2, characterized in that the temperature of the heating of step (2) is between 250 ℃ and 320 ℃ for a time of between 0.5h and 2 h; the heating rate is 5-10 deg.C/min.
7. The method for preparing the structurally-ordered platinum-based intermetallic nanocrystal as claimed in claim 1 or 2, wherein the mass ratio of the carbon powder to the disordered ternary alloy nanoparticles in step (3) is (8-9): (1-2).
8. Structurally ordered platinum-based intermetallic nanocrystals obtainable by the process according to any one of claims 1 to 7.
9. The structurally ordered platinum-based intermetallic nanocrystal of claim 8, wherein the nanocrystal has a diameter of 3nm to 6 nm; the ratio of the amount of platinum atoms, transition metal atoms and low-melting metal atoms in the nanocrystalline is 50: (35-45): (5-15).
10. Use of the structurally ordered platinum-based intermetallic nanocrystals according to claim 8 or 9 for a cathode oxygen reduction catalyst for a proton exchange membrane fuel cell.
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