CN113410483B - 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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CN113410483B
CN113410483B CN202110528990.6A CN202110528990A CN113410483B CN 113410483 B CN113410483 B CN 113410483B CN 202110528990 A CN202110528990 A CN 202110528990A CN 113410483 B CN113410483 B CN 113410483B
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王珏
李冰
张存满
明平文
杨代军
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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 the 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 be mutually diffused, 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, all countries in the world pay great attention to the development and utilization of new energy. As one form of utilization of new energy, the technical development and product popularity of fuel cells have gradually become a research focus 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 method finds that the intermetallic compound is in various intermetallic compoundsThe research results of PtFe and PtCo are the most common. The PtFe intermetallic compounds, hctor D, were prepared, for example, by high temperature treatment, sun watch et al (j.am. Chem.soc.2010,132, 4996-4997) and chard 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) produced PtCo intermetallics of different compositions, respectively, all of which exhibited superior catalytic activity and stability over commercial Pt/C. But a small amount of Fe dissolved out 2+ Will be in contact with H 2 O 2 Fenton 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 larger reserve, wide distribution, low price and catalytic activity which is not inferior to that of PtCo and PtFe, so that the Ni 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 ordered-disordered phase transition temperature of the PtNi phase is lower than 650 ℃, and the ordered structure cannot exist stably above the temperature, so that a longer annealing time is usually required at an excessively high annealing temperature to obtain a higher degree of order, but the sintering of the nanoparticles is aggravated, the activity of the nanoparticles is influenced, the preparation difficulty of the PtNi intermetallic compound is undoubtedly increased, and the research result is relatively rare. For example, yang et al (Nano res.2015,8, 2777-2788) anneal prepared PtNi intermetallic catalyst with specific area activity increased by 3 and 6 times compared to disordered PtNi alloy and commercial Pt/C with minimal loss of performance after durability testing; however, in order to overcome the higher ordering difficulty of PtNi to achieve higher order, the annealing time is as long as 16h, so that the grain size of the sample is increased by 3 times, the ECSA is reduced by 60%, and the specific mass activity is not substantially improved.
In view of the limitation of the potential of catalytic performance of PtNi alloy and the ordering preparation thereof, there is an urgent need for a convenient, effective and widely applicable preparation strategy to promote the ordering process of PtNi alloy, so as to prepare PtNi intermetallic compound catalyst under a relatively mild condition.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an ordering promotion preparation method of a PtNi intermetallic compound catalyst for 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, including 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 co-reduction reaction at 120-220 ℃ for 1-12 h, washing, drying and grinding to obtain the M-PtNi disordered alloy catalyst;
s2: and (2) 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 mutually diffuse, naturally cooling to room temperature, and taking out to obtain the PtNi intermetallic compound catalyst.
Further, the atomic ratio of Pt and Ni in S1 is 1.
Furthermore, the atomic percent of the M element in the S1 accounts for 0.1-33.3 percent of the total amount of the metal atoms.
Further preferably, the atomic percentage of the M element in S1 accounts for 1-20% of the total amount of the metal atoms.
Further preferably, the atomic percentage of the M element in S1 accounts for 5 to 10 percent of the total amount of the metal atoms.
More preferably, the time for the co-reduction reaction in S1 is 2 to 4 hours.
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 other 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 N 2 Ar, 5-8Vol content of H 2 N of (A) 2 Containing 5-8Vol% of H 2 One of Ar of (1).
Further preferably, the M-PtNi random alloy catalyst prepared in S1 is placed in an inert atmosphere at 500 to 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 for 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 the 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 the M-PtNi disordered alloy catalyst;
s2: and (2) placing the M-PtNi disordered alloy catalyst prepared in the S1 in an inert atmosphere at the temperature of 450-650 ℃, preserving 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.
The flow chart 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, preparing an Au-doped supported Au-PtNi disordered alloy catalyst by co-reducing three precursors of Pt, ni and Au. 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 vessel, 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 heat 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 N 2 After purging for 15min, the shielding gas was switched to 5% H 2 And (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 of that of the catalyst reference prepared by the conventional process (comparative example 1).
Through the same ADT cycle, the CV curve and the LSV curve of the PtNi intermetallic compound catalyst prepared in this embodiment change less, which is attributed to that the doping modification process adopted effectively improves the order degree 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 ordering transformation difficulty, and the PtNi intermetallic compound catalyst is prepared by high-temperature annealing treatment, so that the method is taken as an embodiment of the ordering promotion preparation method of the PtNi intermetallic compound catalyst for the fuel cell, and 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. The Au-PtNi/C disordered alloy catalyst prepared in the step 1 is spread on a quartz boat, placed in a tube furnace, provided with a sealing flange,vacuumizing for 15min by N 2 After purging for 15min, the shielding gas was switched to 5% H 2 And (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 such as (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 for 12 hours at 80 ℃, 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 N 2 After purging for 15min, the shielding gas was switched to 5% H 2 And (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 such as (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 carrying out 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 for 12 hours at 80 ℃, 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 order degree. 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 N 2 After purging for 15min, the shielding gas was switched to 5% H 2 And (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, preparing an undoped PtNi disordered alloy catalyst by co-reduction of Pt and Ni double precursors. 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 N 2 After purging for 15min, the shielding gas was switched to 5% H 2 And (3) heating the furnace temperature to 500 ℃ at the heating rate of 8 ℃/min in the/Ar mixed gas, preserving the temperature for 16 hours, and naturally cooling to the 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 (6)

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 a co-reduction reaction at 120-220 ℃ for 1-12 h, washing, drying and grinding to obtain an M-PtNi disordered alloy catalyst, wherein the M element is one of metal organic salt, inorganic salt and acid of Au, and the atomic percent of the M element accounts for 5-10% of the total amount of metal atoms;
s2: placing the M-PtNi disordered alloy catalyst prepared in the S1 in an inert atmosphere at 450-650 ℃, preserving 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 a PtNi intermetallic compound catalyst;
the atomic ratio of Pt to Ni in S1 is 1.
2. The method according to claim 1, wherein the inert atmosphere in S2 is N 2 Ar, 5-8Vol% H 2 N of (A) 2 And contains 5 to 8Vol% of H 2 One of Ar of (1).
3. The method of claim 1, wherein the carbon support comprises one of carbon black, graphite, carbon nanotubes, and carbon nanofibers.
4. The method of claim 1, wherein the Pt and Ni element precursor is one of metal organic salt, inorganic salt, and acid.
5. The method of claim 1, wherein the reducing agent comprises one or more of ethylene glycol, dimethyl amide, oleylamine, and sodium borohydride.
6. A PtNi intermetallic compound catalyst obtained by the production method according to any one of claims 1 to 5.
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Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101436670A (en) * 2007-11-12 2009-05-20 汉能科技有限公司 Fuel battery cathode catalyst and preparation method thereof
RU2367520C1 (en) * 2008-04-07 2009-09-20 Общество с ограниченной ответственностью "НаноХим" Method for fuel cell catalyst preparation
CN102430413B (en) * 2011-10-08 2014-12-10 南京师范大学 PtNi alloy/graphene combined nanometer catalyst with hollow structure and preparation method thereof
CN104475126B (en) * 2014-12-11 2017-10-20 北京化工大学 Fuel cell carbon supported core-shell platinum cobalt platinum catalyst and preparation method thereof
US10099207B2 (en) * 2015-04-02 2018-10-16 Uchicago Argonne, Llc Multimetallic core/interlayer/shell nanoparticles
JP6447739B2 (en) * 2015-09-17 2019-01-09 富士電機株式会社 Perpendicular magnetic recording medium
CN111416132A (en) * 2020-04-03 2020-07-14 北京化工大学 Carbon-supported ordered platinum-copper-nickel catalyst for fuel cell and preparation method thereof
CN112619667B (en) * 2020-12-17 2022-05-13 中国科学技术大学 Sulfur-doped carbon-loaded platinum-based metal oxide interface material, and preparation method and application thereof

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