CN113410483A - Ordering promotion preparation method of PtNi intermetallic compound catalyst of fuel cell and intermetallic compound catalyst - Google Patents

Ordering promotion preparation method of PtNi intermetallic compound catalyst of fuel cell and intermetallic compound catalyst Download PDF

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CN113410483A
CN113410483A CN202110528990.6A CN202110528990A CN113410483A CN 113410483 A CN113410483 A CN 113410483A CN 202110528990 A CN202110528990 A CN 202110528990A CN 113410483 A CN113410483 A CN 113410483A
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王珏
李冰
张存满
明平文
杨代军
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Tongji 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
    • H01M4/90—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to an ordering promotion preparation method of a PtNi intermetallic compound catalyst of a fuel cell and the intermetallic compound catalyst, comprising the following steps: uniformly mixing a Pt precursor, a Ni precursor, an M element precursor for doping modification, a carbon carrier and a reducing agent, carrying out co-reduction reaction at 120-220 ℃ for 1-12 h, washing, drying and grinding to obtain an M-PtNi disordered alloy catalyst; placing the M-PtNi disordered alloy catalyst in an inert atmosphere at 450-650 ℃, preserving heat for 2-20h to enable atoms in the M-PtNi disordered alloy catalyst to mutually diffuse, naturally cooling to room temperature, and taking out to obtain the PtNi intermetallic compound catalyst. Compared with the prior art, the invention adopts an element doping strategy to regulate and control the lattice structure and the interatomic interaction of the PtNi alloy, and reduces the interdiffusion activation energy barrier, thereby promoting the ordered transformation of the PtNi alloy and obtaining the catalyst with high order degree and high performance under a mild condition.

Description

Ordering promotion preparation method of PtNi intermetallic compound catalyst of fuel cell and intermetallic compound catalyst
Technical Field
The invention relates to the field of fuel cells, in particular to an ordering promotion preparation method of a PtNi intermetallic compound catalyst of a fuel cell and the intermetallic compound catalyst.
Background
In order to deal with the problems of resources and environment and adapt to the new change of the energy supply and demand pattern, the development and utilization of new energy are very important for all countries in the world. As one form of new energy utilization, the technological development and product popularity of fuel cells have gradually become a research hotspot in the global energy field. However, the current fuel cell application still faces the limitations of high cost and insufficient performance of key materials such as Pt catalysts. Alloying with 3d transition metal is an effective means for solving the problems of cost and performance of the Pt catalyst of the fuel cell, however, the problems of d-band over-compression, transition metal dissolution loss and the like still exist after the Pt is alloyed with the 3d metal, and the performance and the application of the Pt catalyst are influenced. The metal alloy is different from disordered alloy, and the intermetallic compound is a metal alloy which combines a metal bond and an ionic bond/covalent bond and has an atomic-scale long-range ordered superlattice structure, so that the loss of transition metal can be effectively inhibited while the catalytic activity is better improved.
Through the literature search of the prior art, the research results of PtFe and PtCo are the most common among various intermetallic compounds. The PtFe intermetallic compound, Houctor D, was prepared, for example, by high temperature treatment, Sun Sat et al (J.Am. chem.Soc.2010,132, 4996-4997) and Xid et al (J.Mater. chem.2012,22,6047-6052), respectively.
Figure BDA0003066431700000011
Et al (nat. Mater.2013,12,81-87) and Christopher B.Murray et al (ACS appl. Mater. interfaces 2019,11,26789-26797) respectively prepared PtCo intermetallic compounds with different compositions, and all of the catalysts show excellent catalytic activity and stability over commercial Pt/C. But a small amount of Fe dissolved out2+Will be in contact with H2O2Fenton reaction is carried out to generate strong oxidizing free radicals to attack a proton membrane and an ionomer, so that the battery is invalid; the world reserves, regional distribution and raw material prices of Co are not advantageous, and these problems limit the application of PtFe and PtCo intermetallic catalysts. The other 3d transition metal Ni has large reserve, wide distribution, low cost and catalysisThe activity is not inferior to PtCo and PtFe, so that the PtCo/PtFe alloy has great potential as an intermetallic compound. However, the diffusion coefficient of Ni in Pt is lower than that of Fe and Co, so that the ordering transformation of the PtNi alloy is more difficult, and theoretically, the treatment at higher annealing temperature is favorable for breaking through the high diffusion activation energy barrier; however, the order-disorder phase transition temperature of the PtNi phase is lower than 650 ℃, and the ordered structure cannot stably exist at the temperature, so that the higher order degree can be obtained only by long annealing time at an excessively high annealing temperature, but the sintering of the nanoparticles is aggravated, the activity of the nanoparticles is affected, the preparation difficulty of the PtNi intermetallic compound is increased undoubtedly, and the research result is relatively fresh. For example, Yang et al (Nano Res.2015,8,2777-2788) anneal prepared PtNi intermetallic compound catalyst, compared with disordered PtNi alloy and commercial Pt/C, the area specific activity is improved by 3 times and 6 times, and the performance loss after durability test is minimal; however, in order to overcome the higher ordering difficulty of PtNi to achieve higher order, the annealing time is as long as 16h, which results in the increase of the grain size of the sample by 3 times and the reduction of ECSA by 60%, so that the specific mass activity is not substantially improved.
In view of the potential of catalytic performance of PtNi alloys and the limitation of ordered preparation thereof, there is an urgent need for a convenient, effective and widely applicable preparation strategy to promote the ordering process of PtNi alloys, so as to prepare PtNi intermetallic compound catalysts under mild conditions.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ordering promotion preparation method of a PtNi intermetallic compound catalyst of a fuel cell and the intermetallic compound catalyst.
The purpose of the invention can be realized by the following technical scheme:
a first object of the present application is to protect an ordering promotion preparation method of a PtNi intermetallic compound catalyst for a fuel cell, comprising the steps of:
s1: uniformly mixing a Pt precursor, a Ni precursor, an M element precursor for doping modification, a carbon carrier and a reducing agent, carrying out a co-reduction reaction at the temperature of 120-220 ℃ for 1-12 h, washing, drying and grinding to obtain the M-PtNi disordered alloy catalyst;
s2: and (3) placing the M-PtNi disordered alloy catalyst prepared in the S1 in an inert atmosphere at the temperature of 450-650 ℃, preserving the heat for 2-20h to enable atoms in the M-PtNi disordered alloy catalyst to be mutually diffused, naturally cooling to room temperature, and taking out to obtain the PtNi intermetallic compound catalyst.
Further, the atomic ratio of Pt to Ni in S1 is 1:3 to 3: 1.
Furthermore, the atomic percentage of the M element in the S1 accounts for 0.1-33.3% of the total amount of the metal atoms.
More preferably, the atomic percentage of the M element in the S1 accounts for 1-20% of the total amount of the metal atoms.
More preferably, the atomic percentage of the M element in the S1 accounts for 5-10% of the total amount of the metal atoms.
Further preferably, the time of the co-reduction reaction in S1 is 2-4 h.
Further preferably, the temperature of the co-reduction reaction in S1 is preferably 140 to 200 ℃, particularly 160 to 180 ℃.
Further, the Pt precursor includes, but is not limited to, platinum acetylacetonate, chloroplatinic acid, and the like, or an organic or inorganic salt or acid.
Further, the Ni precursor includes, but is not limited to, nickel acetylacetonate, nickel acetate, nickel chloride, and the like, organic or inorganic salts.
Further, the M element is one of metal organic salt, inorganic salt and acid of Au or Cu.
Further, the inert atmosphere in S2 is N2Ar, 5-8 Vol% H2N of (A)2Containing 5-8 Vol% of H2One of Ar of (1).
Further preferably, the M-PtNi random alloy catalyst prepared in S1 is placed in an inert atmosphere at 500-600 ℃.
Further, the carbon carrier is one of carbon black, graphite, carbon nanotubes and carbon nanofibers.
Further preferably, the carbon carrier is one of Vulcan XC-72, multi-walled carbon nanotube, single-walled carbon nanotube.
Further preferably, the carbon support is Vulcan XC-72.
Furthermore, the mass of the carbon carrier in the technical scheme is reasonably valued, and sufficient load can be realized.
Further, the reducing agent is one or more of ethylene glycol, dimethyl amide, oleylamine and sodium borohydride.
A second object of the present application is to protect a PtNi intermetallic compound catalyst obtained by the preparation method as described above.
Compared with the prior art, the invention has the following technical advantages:
1) compared with the prior art, the invention adopts an element doping strategy to regulate and control the lattice structure and the interatomic interaction of the PtNi alloy, and reduces the interdiffusion activation energy barrier, thereby promoting the ordered transformation of the PtNi alloy and obtaining the catalyst with high order degree and high performance under a mild condition.
2) The process disclosed by the invention not only can overcome the difficulty in preparing the PtNi intermetallic compound and promote the application of the PtNi intermetallic compound in the field of catalysts, but also can provide reference for improving the preparation schemes of other Pt-based intermetallic compounds.
Drawings
Fig. 1 is a flowchart of an ordering promotion preparation method of a PtNi intermetallic compound catalyst of a fuel cell according to the present embodiment;
fig. 2 is an XRD spectrum of the PtNi intermetallic compound prepared before and after Au doping (corresponding to example 1 and comparative example 1);
FIG. 3 is a comparison of ORR activity and durability of PtNi/C catalysts before and after Au doping (corresponding to example 1 and comparative example 1).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The ordered promotion preparation method of the PtNi intermetallic compound catalyst for the fuel cell in the technical scheme comprises the following steps:
s1: uniformly mixing a Pt precursor, a Ni precursor, an M element precursor for doping modification, a carbon carrier and a reducing agent, carrying out co-reduction reaction at 120-220 ℃ for 1-12 h, washing, drying and grinding to obtain an M-PtNi disordered alloy catalyst;
s2: and (3) placing the M-PtNi disordered alloy catalyst prepared in the S1 in an inert atmosphere at the temperature of 450-650 ℃, preserving the heat for 2-20 hours to enable atoms in the M-PtNi disordered alloy catalyst to mutually diffuse, naturally cooling to room temperature, and taking out to obtain the PtNi intermetallic compound catalyst.
A flowchart of the above steps can be seen in fig. 1.
Example 1
The method is adopted to carry out Au doping modification in the process of preparing the PtNi disordered alloy by an ethylene glycol reduction method, so as to reduce the difficulty of ordering transformation, and the PtNi intermetallic compound catalyst is prepared by high-temperature annealing treatment, so that the embodiment of the ordering promotion preparation method of the PtNi intermetallic compound catalyst for the fuel cell specifically comprises the following steps:
step 1, co-reducing Pt, Ni and Au three precursors to prepare the supported Au-PtNi disordered alloy catalyst doped with the Au element. Dissolving platinum acetylacetonate, nickel acetylacetonate and chloroauric acid in 20mL of ethylene glycol, taking 20mL of ethylene glycol to ultrasonically disperse Vulcan XC-72 carbon carrier, mixing the two dispersed solutions, and continuously performing ultrasonic treatment for 30min to obtain a uniform mixed solution, wherein the mixed solution contains 9.5mM of platinum acetylacetonate, 9.5mM of nickel acetylacetonate and 1.0mM of chloroauric acid, and the mass of the carbon carrier is 1.5 times of the Pt content in the precursor. And transferring the mixed solution to a normal-pressure reaction container, vacuumizing, introducing nitrogen for 30min to remove air in the system, keeping stirring, raising the temperature from room temperature to 170 ℃ under the protection of nitrogen, preserving the temperature for 2h, and naturally cooling to room temperature. And (3) carrying out suction filtration and cleaning on the product by using an ethanol/deionized water mixed solvent until the filtrate has no chloride ions, carrying out vacuum drying at 80 ℃ for 12h, and grinding to obtain the Au-PtNi/C disordered alloy catalyst with the Au content of 5 at.%.
And 2, carrying out high-temperature annealing treatment on the Au-PtNi/C disordered alloy catalyst to obtain the PtNi intermetallic compound catalyst with high degree of order. Will be described in detail1, spreading the Au-PtNi/C disordered alloy catalyst prepared in the step 1 on a quartz boat, placing the quartz boat in a tube furnace, installing a sealing flange, vacuumizing for 15min, and adding N2After purging for 15min, the shielding gas was switched to 5% H2And (3) heating the furnace temperature to 500 ℃ at the heating rate of 8 ℃/min by using the/Ar mixed gas, preserving the temperature for 16h, and naturally cooling to room temperature to obtain the ordered PtNi intermetallic compound catalyst.
As shown in fig. 2, the samples prepared in this example had diffraction peaks of (110), (201), (112), and the like of a face-centered tetragonal (fct) structure, indicating that the ordered intermetallic compound was formed; under the same conditions, the Au-doped sample (110) peak prepared by the ordering promotion process is obviously enhanced, and the (111) peak is weakened, so that the ordering degree in proportion to the intensity ratio of the two peaks is obviously higher than that of a reference prepared by the traditional process (comparative example 1), and the doping modification process disclosed by the invention is proved to be capable of effectively promoting the ordering transformation of the PtNi alloy, and is beneficial to obtaining higher ordering degree of the sample under milder conditions (such as shorter annealing time) so as to ensure the size and the performance of the sample.
As shown in fig. 3, the mass specific activity of the PtNi intermetallic compound catalyst prepared in this example was improved to 1.36 times as compared with the catalyst reference prepared by the conventional process (comparative example 1).
Through the same ADT cycle, the change of CV and LSV curves of the PtNi intermetallic compound catalyst prepared in this embodiment is smaller, which is attributed to that the adopted doping modification process effectively improves the degree of order thereof, so that higher stability and performance retention rate are obtained, and it is proved that the doping modification ordering promotion process of the present invention can well give consideration to the improvement of catalytic activity and durability of the PtNi intermetallic compound catalyst.
Example 2
The method is adopted to carry out Au doping modification in the process of preparing the PtNi disordered alloy by an oil amine reduction method, so as to reduce the difficulty of ordering transformation, and the PtNi intermetallic compound catalyst is prepared by high-temperature annealing treatment, so that the embodiment of the ordering promotion preparation method of the PtNi intermetallic compound catalyst for the fuel cell specifically comprises the following steps:
step 1, co-reducing Pt, Ni and Au three precursors to prepare the supported Au-PtNi disordered alloy catalyst doped with the Au element. Dissolving platinum acetylacetonate, nickel acetylacetonate and chloroauric acid in 20mL of oleylamine, taking 20mL of oleylamine to ultrasonically disperse Vulcan XC-72 carbon carrier, mixing the two dispersed solutions, and continuously performing ultrasonic treatment for 30min to obtain a uniform mixed solution, wherein the mixed solution contains 14.25mM of platinum acetylacetonate, 4.75mM of nickel acetylacetonate and 1.0mM of chloroauric acid, and the mass of the carbon carrier is 1.5 times of the Pt content in the precursor. And transferring the mixed solution to a normal-pressure reaction container, vacuumizing, introducing nitrogen for 30min to remove air in the system, keeping stirring, raising the temperature from room temperature to 200 ℃ under the protection of nitrogen, preserving the temperature for 2h, and naturally cooling to room temperature. And (3) carrying out suction filtration and cleaning on the product by using an ethanol/deionized water mixed solvent until the filtrate has no chloride ions, carrying out vacuum drying at 80 ℃ for 12h, and grinding to obtain the Au-PtNi/C disordered alloy catalyst with the Au content of 5 at.%.
And 2, carrying out high-temperature annealing treatment on the Au-PtNi/C disordered alloy catalyst to obtain the PtNi intermetallic compound catalyst with high degree of order. Spreading the Au-PtNi/C disordered alloy catalyst prepared in the step 1 on a quartz boat, placing the quartz boat in a tube furnace, installing a sealing flange, vacuumizing for 15min, and adding N2After purging for 15min, the shielding gas was switched to 5% H2And (3) heating the furnace temperature to 500 ℃ at the heating rate of 8 ℃/min by using the/Ar mixed gas, preserving the temperature for 16h, and naturally cooling to room temperature to obtain the ordered PtNi intermetallic compound catalyst.
The sample prepared in this example had diffraction peaks of (110), (201), (112), and the like of a face-centered tetragonal (fct) structure, indicating that the ordered intermetallic compound was formed.
The change of CV and LSV curves of the PtNi intermetallic compound catalyst prepared in this embodiment is very small after the same ADT cycle, which is attributed to the fact that the adopted doping modification process effectively improves the degree of order, so that higher stability and performance retention rate are obtained, and it is proved that the doping modification ordering promotion process of the present invention can well give consideration to the improvement of catalytic activity and durability of the PtNi intermetallic compound catalyst.
Example 3
The method is adopted to carry out Au doping modification in the process of preparing the PtNi disordered alloy by an ethylene glycol reduction method, so as to reduce the difficulty of ordering transformation, and the PtNi intermetallic compound catalyst is prepared by high-temperature annealing treatment, so that the embodiment of the ordering promotion preparation method of the PtNi intermetallic compound catalyst for the fuel cell specifically comprises the following steps:
step 1, co-reducing Pt, Ni and Au three precursors to prepare the supported Au-PtNi disordered alloy catalyst doped with the Au element. Dissolving platinum acetylacetonate, nickel acetylacetonate and chloroauric acid in 20mL of ethylene glycol, taking 20mL of ethylene glycol to ultrasonically disperse Vulcan XC-72 carbon carrier, mixing the two dispersed solutions, and continuing to ultrasonically process for 30min to obtain a uniform mixed solution, wherein the mixed solution contains 4.75mM of platinum acetylacetonate, 14.25mM of nickel acetylacetonate and 1.0mM of chloroauric acid, and the mass of the carbon carrier is 1.5 times of the Pt content in the precursor. And transferring the mixed solution to a normal-pressure reaction container, vacuumizing, introducing nitrogen for 30min to remove air in the system, keeping stirring, raising the temperature from room temperature to 170 ℃ under the protection of nitrogen, preserving the temperature for 2h, and naturally cooling to room temperature. And (3) carrying out suction filtration and cleaning on the product by using an ethanol/deionized water mixed solvent until the filtrate has no chloride ions, carrying out vacuum drying at 80 ℃ for 12h, and grinding to obtain the Au-PtNi/C disordered alloy catalyst with the Au content of 5 at.%.
And 2, carrying out high-temperature annealing treatment on the Au-PtNi/C disordered alloy catalyst to obtain the PtNi intermetallic compound catalyst with high degree of order. Spreading the Au-PtNi/C disordered alloy catalyst prepared in the step 1 on a quartz boat, placing the quartz boat in a tube furnace, installing a sealing flange, vacuumizing for 15min, and adding N2After purging for 15min, the shielding gas was switched to 5% H2And (3) heating the furnace temperature to 500 ℃ at the heating rate of 8 ℃/min by using the/Ar mixed gas, preserving the temperature for 16h, and naturally cooling to room temperature to obtain the ordered PtNi intermetallic compound catalyst.
The sample prepared in this example had diffraction peaks of (110), (201), (112), and the like of a face-centered tetragonal (fct) structure, indicating that the ordered intermetallic compound was formed.
The change of CV and LSV curves of the PtNi intermetallic compound catalyst prepared in this embodiment is very small after the same ADT cycle, which is attributed to the fact that the adopted doping modification process effectively improves the degree of order, so that higher stability and performance retention rate are obtained, and it is proved that the doping modification ordering promotion process of the present invention can well give consideration to the improvement of catalytic activity and durability of the PtNi intermetallic compound catalyst.
Example 4
The method is adopted to carry out Au doping modification in the process of preparing the PtNi disordered alloy by an ethylene glycol reduction method, so as to reduce the difficulty of ordering transformation, and the PtNi intermetallic compound catalyst is prepared by high-temperature annealing treatment, so that the embodiment of the ordering promotion preparation method of the PtNi intermetallic compound catalyst for the fuel cell specifically comprises the following steps:
step 1, co-reducing Pt, Ni and Au three precursors to prepare the supported Au-PtNi disordered alloy catalyst doped with the Au element. Dissolving platinum acetylacetonate, nickel acetylacetonate and chloroauric acid in 20mL of ethylene glycol, taking 20mL of ethylene glycol to ultrasonically disperse Vulcan XC-72 carbon carrier, mixing the two dispersed solutions, and continuously performing ultrasonic treatment for 30min to obtain a uniform mixed solution, wherein the mixed solution contains 9.0mM of platinum acetylacetonate, 9.0mM of nickel acetylacetonate and 2.0mM of chloroauric acid, and the mass of the carbon carrier is 1.5 times of the Pt content in the precursor. And transferring the mixed solution to a normal-pressure reaction container, vacuumizing, introducing nitrogen for 30min to remove air in the system, keeping stirring, raising the temperature from room temperature to 170 ℃ under the protection of nitrogen, preserving the temperature for 2h, and naturally cooling to room temperature. And (3) carrying out suction filtration and cleaning on the product by using an ethanol/deionized water mixed solvent until the filtrate has no chloride ions, carrying out vacuum drying at 80 ℃ for 12h, and grinding to obtain the Au-PtNi/C disordered alloy catalyst with the Au content of 10 at.%.
And 2, carrying out high-temperature annealing treatment on the Au-PtNi/C disordered alloy catalyst to obtain the PtNi intermetallic compound catalyst with high degree of order. Spreading the Au-PtNi/C disordered alloy catalyst prepared in the step 1 on a quartz boat, placing the quartz boat in a tube furnace, installing a sealing flange, vacuumizing for 15min, and adding N2After purging for 15min, the shielding gas was switched to 5% H2And (3) heating the furnace temperature to 500 ℃ at the heating rate of 8 ℃/min by using the/Ar mixed gas, preserving the temperature for 16h, and naturally cooling to room temperature to obtain the ordered PtNi intermetallic compound catalyst.
The sample prepared in this example had diffraction peaks of (110), (201), (112), and the like of a face-centered tetragonal (fct) structure, indicating that the ordered intermetallic compound was formed.
The change of CV and LSV curves of the PtNi intermetallic compound catalyst prepared in this embodiment is very small after the same ADT cycle, which is attributed to the fact that the adopted doping modification process effectively improves the degree of order, so that higher stability and performance retention rate are obtained, and it is proved that the doping modification ordering promotion process of the present invention can well give consideration to the improvement of catalytic activity and durability of the PtNi intermetallic compound catalyst.
Comparative example 1
Step 1, co-reducing Pt and Ni double precursors to prepare the undoped PtNi disordered alloy catalyst. Dissolving platinum acetylacetonate and nickel acetylacetonate in 20mL of ethylene glycol, taking 20mL of ethylene glycol to ultrasonically disperse Vulcan XC-72 carbon carrier, mixing the two dispersed solutions, and continuously performing ultrasonic treatment for 30min to obtain a uniform mixed solution, wherein the mixed solution contains 9.5mM of platinum acetylacetonate and 9.5mM of nickel acetylacetonate, and the mass of the carbon carrier is 1.5 times of the Pt content in the precursor. And transferring the mixed solution to a normal-pressure reaction container, vacuumizing, introducing nitrogen for 30min to remove air in the system, keeping stirring, raising the temperature from room temperature to 170 ℃ under the protection of nitrogen, preserving the temperature for 2h, and naturally cooling to room temperature. And (3) carrying out suction filtration and cleaning on the product by using an ethanol/deionized water mixed solvent until filtrate has no chloride ions, carrying out vacuum drying at 80 ℃ for 12h, and grinding to obtain the PtNi/C disordered alloy catalyst.
And 2, carrying out high-temperature annealing treatment on the PtNi/C disordered alloy catalyst to obtain the PtNi intermetallic compound catalyst. Flatly paving the PtNi/C disordered alloy catalyst prepared in the step 1 on a quartz boat, placing the quartz boat in a tube furnace, installing a sealing flange, vacuumizing for 15min, and adding N2After purging for 15min, the shielding gas was switched to 5% H2And (4) heating the furnace temperature to 500 ℃ at the heating rate of 8 ℃/min by using the/Ar mixed gas, preserving the temperature for 16h, and naturally cooling to room temperature to obtain the PtNi intermetallic compound catalyst.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. An ordering promotion preparation method of a PtNi intermetallic compound catalyst of a fuel cell is characterized by comprising the following steps:
s1: uniformly mixing a Pt precursor, a Ni precursor, an M element precursor for doping modification, a carbon carrier and a reducing agent, carrying out co-reduction reaction at 120-220 ℃ for 1-12 h, washing, drying and grinding to obtain an M-PtNi disordered alloy catalyst;
s2: and (3) placing the M-PtNi disordered alloy catalyst prepared in the S1 in an inert atmosphere at the temperature of 450-650 ℃, preserving the heat for 2-20 hours to enable atoms in the M-PtNi disordered alloy catalyst to mutually diffuse, naturally cooling to room temperature, and taking out to obtain the PtNi intermetallic compound catalyst.
2. The ordering-promoted preparation method of a PtNi intermetallic compound catalyst for a fuel cell according to claim 1, characterized in that the atomic ratio of Pt and Ni in S1 is 1:3 to 3: 1.
3. The method of claim 1, wherein the atomic percentage of the M element in S1 is 0.1-33.3% of the total metal atoms.
4. The method for orderly promoting the preparation of the PtNi intermetallic compound catalyst for the fuel cell according to claim 3, wherein the atomic percent of the M element in S1 accounts for 1-20% of the total amount of the metal atoms.
5. The method according to claim 3, wherein the M element precursor is one of a metal organic salt, an inorganic salt, and an acid.
6. The method according to claim 1, wherein the inert atmosphere in S2 is N2Ar, 5-8 Vol% H2N of (A)2And contains 5 to 8 Vol% of H2One of Ar of (1).
7. The method of claim 1, wherein the carbon support comprises one of carbon black, graphite, carbon nanotubes, and carbon nanofibers.
8. The method of claim 1, wherein the Pt and Ni element precursor is one of metal organic salt, inorganic salt, and acid.
9. The method of claim 1, wherein the reducing agent comprises one or more of ethylene glycol, dimethyl amide, oleylamine, and sodium borohydride.
10. A PtNi intermetallic compound catalyst obtained by the production method according to any one of claims 1 to 9.
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