CN114094130B - Preparation method of fuel cell platinum alloy catalyst - Google Patents
Preparation method of fuel cell platinum alloy catalyst Download PDFInfo
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- CN114094130B CN114094130B CN202111438645.XA CN202111438645A CN114094130B CN 114094130 B CN114094130 B CN 114094130B CN 202111438645 A CN202111438645 A CN 202111438645A CN 114094130 B CN114094130 B CN 114094130B
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/925—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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a preparation method of a novel fuel cell low-platinum alloy catalyst, which is prepared by mixing platinum (II) acetylacetonate, zinc acetylacetonate hydrate and polyvinylpyrrolidoneAdding alkanone into mixed solution of benzyl alcohol and acetaldehyde, heating to 160-200 deg.C, maintaining the temperature for 8-10 hr, cooling to room temperature, centrifuging, washing, drying at 60 deg.C overnight, and loading on Ketjen black. The concave Pt-Zn nanocubes have high-index platinum crystal faces and can reduce OH ＊ /O ＊ Adsorption energy on the surface of Pt. In addition, the Fenton-resistant zinc and platinum-rich surface engineering have good synergistic effect, and the Fenton-resistant zinc has the advantages of 1.18 mA mu gPt ‑1 The mass activity of (2) was 3.89 mA cm at 0.9V (relative to RHE) ‑2 Specific activity of (3). H assembled from the catalyst 2 ‑O 2 The fuel cell has ultrahigh peak power density of 1449 mW cm ‑2 The performance is superior to commercial Pt/C.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material chemistry and electrochemistry, and particularly relates to a preparation method of a novel low-platinum alloy catalyst for a fuel cell and application of the catalyst in improving the performance of a proton exchange membrane fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are a highly attractive and efficient alternative to the combustion of energy from huaneng energy sources (j. Tollefson,Nature2010, 464, 1262.). However, the slow kinetics of the cathodic Oxygen Reduction Reaction (ORR) and the use of platinum (Pt) -based materials as the most active and stable ORR catalysts have been the reasons that have severely hampered their commercialization (s. Guo, s. Zhang, s. Sun,Angew. Chem. Int. Ed.2013, 52, 8526.). However, platinum has low earth reserves and high cost, which makes it impossible to achieve wide application. Platinum-based metal-transition metal (Pt-M), particularly catalysts combined with 3d transition metals (Fe, ni, co, cu, etc.) (y. Yoo, j.m. Yoo, et al,J. Am. Chem. Soc. 2020, 142, 14190.) increasing activity of Pt while decreasing Pt loading by adding a transition metal. These alloyed transition metals inevitably dissolve during actual operation of the pem fuel cell, resulting in metal ions reacting with H generated during the process 2 O 2 In combination, the Fenton reaction that occurs during this process degrades the proton exchange membrane, generating aggressive OH radicals. In addition, the resulting metal ions reduce the conductivity of the proton exchange membrane (a.d. Bokare, w. Choi,J. Hazard. Mater.2014, 275, 121.). Among these transition metal elements, zn has a better oxidation resistance and can effectively inhibit the fenton reaction, thereby improving the stability of the Pt-based catalyst.
Recently, considerable work has focused on adjusting the structure, composition and morphology (n. Becknell, y. Son, d. Kim, et al,J. Am. Chem. Soc. 2017, 139, 11678.). It is well known that catalytic reactions typically occur on the surface of the catalyst, and therefore the surface structure plays a crucial role in determining performance (c. Xiao, b. -a. Lu, et al,Joule2020, 4, 2562.) the oxygen reduction reaction is a surface structure sensitive reaction, whereas the step surface is more active than the low index plane (n. -f. Yu, n. Tian, et al,ACS Catal.2019, 9, 3144.). Thus, another important strategy to improve catalytic activity is to tailor metal nanocrystals with high index facets. Atoms located at the steps, plateaus and kinks of the high index nanocrystal can act as catalytically active centers (n. Tians, z.y. Zhou, s.g. Sun, y. Ding, z.l. Wang,Science 2007, 316, 732)), which is advantageous for improving the catalytic activity. (L, huang, M, liu, et al,Science2019, 365, 1159.). However, to date, there has been no clear design using ultra-thin platinum surfaces and high index multi-faceted synergy for efficient platinum-zinc based ORR catalysts. Therefore, the method selects a combination strategy of platinum skin and a high-index crystal face structure aiming at high ORR performance, develops a high-activity and low-cost platinum-zinc-based catalyst, and provides a new design scheme for the platinum alloy catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a novel low-platinum alloy catalyst for a fuel cell, wherein OH can be reduced through a high-index platinum crystal face of a concave Pt-Zn nanocube ＊ /O ＊ The adsorption energy on the platinum surface improves the activity and stability of the acidic ORR.
The invention also provides a preparation method of the novel fuel cell low platinum alloy catalyst and application of the novel fuel cell low platinum alloy catalyst in improving the performance of a proton exchange membrane fuel cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a novel fuel cell low-platinum alloy catalyst comprises the steps of uniformly dispersing platinum (II) acetylacetonate, zinc acetylacetonate hydrate and polyvinylpyrrolidone into a mixed solution of benzyl alcohol and acetaldehyde, heating to 160-200 ℃, keeping the temperature for 8-10 hours, cooling to room temperature, centrifuging, washing, drying to obtain Pt-Zn nanocrystals, and loading the Pt-Zn nanocrystals on Ketjen black.
Specifically, the mass ratio of platinum (II) acetylacetonate, zinc acetylacetonate hydrate, and polyvinylpyrrolidone may be 1:1.2-1.3:13-18, preferably 1:1.25:15. further, the volume ratio of benzyl alcohol to acetaldehyde is 1:1. significant changes in the ratio can affect the internal structure and properties of the material product. 20mg of zinc acetylacetonate hydrate and 240mg of polyvinylpyrrolidone were added to 16mg of platinum (II) acetylacetonate. After the same proportional amount of expansion, the performance is not changed significantly.
Further, the preparation method of the novel fuel cell low platinum alloy catalyst is specifically prepared by the following steps:
1) Uniformly mixing benzyl alcohol and acetaldehyde to form a first mixed solution; generally, the method is carried out for 30min under the room temperature condition by magnetic stirring, the benzyl alcohol cannot be uniformly dispersed when the stirring time is too short, and the uniform dispersion degree of the benzyl alcohol cannot be continuously improved after the stirring is carried out for a certain time;
2) Adding acetylacetone platinum (II), hydrated acetylacetone zinc and polyvinylpyrrolidone into the first mixed solution, and uniformly mixing to form a second mixed solution; stirring vigorously in general (1000 r min) -1 1 h) mixing uniformly; the stirring time is too short, and the stirring force is too small, so that the platinum (II) acetylacetonate and the hydrated zinc acetylacetonate cannot be fully mixed;
3) Transferring the second mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining; sealing and heating the reaction kettle to 180 ℃, keeping the temperature for 8 hours, and naturally cooling to room temperature to obtain a third mixed solution;
4) Centrifuging the third mixed solution, washing with a mixed solution of cyclohexane and ethanol, and collecting the obtained product;
5) Washing the obtained product with glacial acetic acid, centrifuging, collecting, washing with ethanol for several times, and drying at 60 ℃ overnight to obtain Pt-Zn nanocrystalline; loading Pt-Zn nanocrystalline on Ketjen black to obtain the final product. It is a concave Pt-Zn nanocube with a high-index platinum crystal face capable of reducing OH ＊ /O ＊ Adsorption energy on the surface of Pt; moreover, the antioxidant metal zinc and the platinum-rich surface engineering have good synergistic effect, and the antioxidant metal zinc has the thickness of 1.18 mA mu gPt -1 The mass activity of (2) was 3.89 mA cm at 0.9V (relative to RHE) -2 Specific activity of (3). H assembled from the catalyst 2 -O 2 The fuel cell has ultrahigh peak power density of 1449 mW cm -2 The performance is superior to commercial Pt/C.
Specifically, in the step 1), the volume ratio of benzyl alcohol to acetaldehyde is 1:0.5-2.
Specifically, in step 3), the temperature is increased from room temperature to 180 ℃ within 30 min.
Specifically, in the step 4), the volume ratio of cyclohexane to ethanol is 0.5-2:1. the centrifugation speed is preferably 11000 rpm, and the centrifugation time is preferably 10 min. The Pt-Zn nanocrystalline is loaded on the Ketjen black, and specifically comprises the following components: mixing platinum zinc nanocrystalline and Ketjen black with deionized water, transferring into a high-pressure reaction kettle, sealing the reaction kettle, maintaining at 180-200 deg.C for 8-10h, naturally cooling to room temperature, centrifuging, collecting, and drying.
The invention provides a preparation method of the novel fuel cell low platinum alloy catalyst prepared by the preparation method.
The invention also provides the application of the novel fuel cell low platinum alloy catalyst in a proton exchange membrane fuel cell.
As the proton exchange membrane fuel cell inevitably dissolves basic metal in the operation process, the generated metal cations generate aggressive OH free radicals through substituting protons and catalyzing Fenton reaction, thereby causing the degradation of the proton exchange membrane. Among these transition metal elements, zn has a good oxidation resistance, and can effectively inhibit the fenton reaction, thereby improving the stability of the Pt-based catalyst. The catalytic reaction usually takes place at the surface of the catalyst, and the surface structure therefore plays a crucial role in the performance of the catalyst. Previous studies also give clear images of the sensitivity of the ORR structure and reveal the surface adsorption behavior of oxygen species, with the step surface being more active than the low index plane. Another important strategy to improve catalytic activity is to tailor metal nanocrystals with high index facets. Atoms at the steps, steps and kinks of the high-index nanocrystal can be used as additional catalytic active centers, which is beneficial to catalysis.
Based on the method, the novel low-platinum alloy catalyst for the fuel cell is prepared by a simple and universal method under mild conditions, and has high acidic ORR activity and stability. Both experiments and theoretical calculation show that the introduction of Zn adjusts the electronic structure of the Pt surface, thereby shortening the length of Pt-Pt bonds and reducing the adsorption energy of OH/O on the Pt surface. H assembled from the catalyst 2 -O 2 The fuel cell provides about 1449 mW cm -2 The peak power density is higher than that of Pt/C catalyst. This is the highest performance of fuel cells based on Pt-Zn catalysts.
The concave platinum-zinc nanocubes with high-index crystal face platinum skin are prepared by a solvothermal method. The formation of such high index Pt-Zn catalysts is based on the reduction capability of aldehyde groups in a solvothermal reaction. The concave nanocube shape provides more active surface structures such as atomic steps and edges, and also improves platinum utilization. The test results show that: pt-Zn/KB shows significant acidic ORR activity and expected stability. Compared with the prior art, the invention has the beneficial effects that:
1) The invention provides a synthetic route for preparing a novel fuel cell low-platinum alloy catalyst material. The target product Pt-Zn/KB is prepared by a simple hydrothermal method;
2) The invention has simple preparation process and is easy for batch preparation. Meanwhile, the novel low platinum alloy catalyst material for the fuel cell, which is obtained by the invention, has excellent electrochemical performance;
3) The novel fuel cell low-platinum alloy catalyst material prepared by the invention can improve the electronic structure of the Pt surface and enhance the catalytic performance.
Drawings
FIG. 1 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) of the novel fuel cell low platinum alloy catalyst material Pt-Zn/KB-1 prepared in example 1, with a scale bar of 20 nm;
FIG. 2 is a TEM image of Pt-Zn/KB-2 as a catalyst material obtained in comparative example 1, wherein (a) and (b) are TEM images on different scales of 20nm and 5nm, respectively;
FIG. 3 is a TEM image of pure Pt/KB as the catalyst material prepared in comparative example 2, wherein (a) and (b) are TEM images at different scales of 20nm and 5 nm;
FIG. 4 is an X-ray diffraction (XRD) pattern of the catalyst material Pt-Zn/KB-1 prepared in example 1;
FIG. 5 shows the results of catalyst materials Pt-Zn/KB-1, pt-Zn/KB-2, pure Pt/KB and commercial Pt/C (20%) prepared in example 1, comparative example 1 and comparative example 2 at 0.1M HClO 4 CV curve (a) tested in solution, LSV curve (b) at 1600rpm/min, LSV curve (c) cycled at 1600rpm/min with a sweep rate of 50mV/s over 30000 cycles, and acid fuel cell data (d) tested for Pt-Zn/KB-1, the catalyst material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the invention, all the raw materials are common commercial products which can be directly purchased in the field.
Example 1
The preparation method of the novel fuel cell low platinum alloy catalyst specifically comprises the following steps:
1) Uniformly mixing 6mL benzyl alcohol and 6mL acetaldehyde to form a first mixed solution;
2) 16mg of platinum (II) acetylacetonate, 20mg of zinc acetylacetonate hydrate and 240mg of polyvinylpyrrolidone are respectively weighed and then added into the first mixed solution, and the mixed solution is vigorously stirred (1000 r min) -1 ) Stirring for 1 hour to form a uniform second mixed solution;
3) Transferring the second mixed solution into a 25mL high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle to 180 ℃ from room temperature within 30min, keeping the temperature for 8h, and naturally cooling the reaction kettle to room temperature to obtain a third mixed solution;
4) Centrifuging the third mixed solution at 12000 r/min for 10 min, collecting the product, washing with cyclohexane and ethanol (in a volume ratio of 1:1) for three times, and collecting the obtained product;
5) Washing the obtained product with glacial acetic acid (80 ℃,4 h), centrifuging, collecting, washing with ethanol for several times, and drying at 60 ℃ overnight (12 h) to obtain Pt-Zn nanocrystalline;
6) Uniformly mixing the platinum-zinc nanocrystalline particle product obtained in the step 5) and Keqin black (the mass of the Keqin black is 2 times of that of the platinum-zinc nanocrystalline particle product) with 16mL of deionized water, and vigorously stirring the mixed solution (1000 r min) -1 ) Forming a uniform solution No. four in 1 hour; transferring the solution IV into a 25mL high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating to 180 ℃ from room temperature within 30min, keeping the temperature for 8h, naturally cooling to room temperature, centrifugally collecting, and drying at 60 ℃ overnight (12 h) to obtain a Pt-Zn/KB-1 product.
Comparative example 1
A method for preparing a fuel cell low platinum alloy catalyst, which is different from that of example 1 in that: in step 2), the dosage of the platinum (II) acetylacetonate is 16mg, the dosage of the zinc acetylacetonate hydrate is 10mg, and the prepared product is marked as PtZn/KB-2.
Comparative example 2
A method for preparing a fuel cell low platinum alloy catalyst, which is different from the method of the embodiment 1 in that: the amount of platinum (II) acetylacetonate used in step 2) was 16mg, and no zinc acetylacetonate was added, and the product obtained was designated as pure Pt/KB.
And (4) relevant testing:
fuel cell low platinum alloy catalyst Pt prepared in example 1, comparative example 1 and comparative example 2 - Transmission Electron Micrographs (TEM) of Zn/KB-1, pt-Zn/KB-2 and pure Pt/KB are shown in FIG. 1, FIG. 2 and FIG. 3, respectively.
FIG. 1 is a HAADF-STEM diagram with a resolution of 20 nm. The characterization results of fig. 1 show that: ketjen black is used as a substrate, the obtained catalyst Pt-Zn/KB-1, ptZn nanoparticles are uniformly distributed on the carbon substrate, and the particle size of the nanoparticles is 10-15nm.
In FIG. 2, (a) and (b) are TEM images at different resolutions, and the scales are 20nm and 5nm, respectively. The characterization results of fig. 2 show that: the catalyst Pt-Zn/KB-2, ptZn nano-particles are uniformly distributed on the carbon substrate by adopting Ketjen black as the substrate, and the particle size of the nano-particles is about 5nm.
The characterization results of fig. 3 show that: the Ketjen black is used as a substrate, the obtained catalyst is pure Pt/KB, pt nanoparticles are uniformly distributed on the carbon substrate, and the particle size of the nanoparticles is about 7nm.
The X-ray diffraction (XRD) of the catalyst material Pt-Zn/KB-1 obtained in example 1 is shown in FIG. 4. By comparing with the standard XRD patterns of Pt and Zn, the prepared product is a Pt-Zn crystal. There was a slight right shift relative to Pt (JCPDS No. 04-0802), indicating the incorporation of Zn atoms into the Pt lattice.
Catalyst materials Pt-Zn/KB-1, pt-Zn/KB-2, pure Pt/KB and commercial Pt/C (20%) prepared in example 1, comparative example 1 and comparative example 2 were in 0.1M HClO 4 The CV curve tested in solution is shown in FIG. 5 (a). Catalyst materials Pt-Zn/KB-1, pt-Zn/KB-2, pure Pt/KB and commercial Pt/C (20%) prepared in example 1, comparative example 1 and comparative example 2 were in 0.1M HClO 4 The LSV curve at 1600rpm/min tested in solution is shown in FIG. 5 (b). EXAMPLE 1 catalyst Pt-Zn/KB-1 prepared according to example 1 and commercial Pt/C (20%) LSV curves (0.1M HClO) cycled over 30000 cycles at 1600rpm/min with a sweep rate of 50mV/s 4 Solution) is shown in fig. 5 (c). Oxygen (O)The reduction reaction test environment was at 0.1M HClO 4 In solution. From FIG. 5 (a), it can be seen that Pt-Zn/KB-1 has a significant reduction peak at 0.88V. And it can be seen from FIG. 5 (b) that the half-wave potential (0.914V) of the catalyst Pt-Zn/KB-1 is much higher than that of the material prepared in comparative example 1 (0.751V) and comparative example 2 (0.872V) and that commercial Pt/C (20%) (0.88V). As can be seen from FIG. 5 (b), the half-wave potential of the catalyst Pt-Zn/KB-1 is 0.914V, which is much higher than the half-wave potential (0.88V) of the commercial Pt/C (20%), indicating that the catalyst has high catalytic performance in the ORR reaction process.
The oxygen reduction reaction test adopts a three-electrode test system, namely a platinum sheet is used as a counter electrode, ag/AgCl is used as a reference electrode, a glassy carbon electrode is used as a working electrode, and the performance is tested by adopting the three-electrode system. Specifically, the catalyst materials prepared in example 1, comparative example 2 and comparative example 3 were supported on a glassy carbon electrode. The method for experimental loading of catalyst material onto a glassy carbon electrode was: taking a 5.0 mg catalyst sample, dissolving in a solution prepared from 336.0 muL ethanol, 144.0 muL deionized water and 20 muL naphthol; and (3) uniformly mixing the prepared solution by ultrasonic waves for 30min, measuring 5.0 mu L of the mixed solution by using a liquid-transferring gun, vertically dripping the mixed solution on a glassy carbon electrode, and naturally drying the glassy carbon electrode to obtain the working electrode. FIG. 5 (C) is the LSV curve (0.1M HClO) before and after 30000 cycles of Pt-Zn/KB-1 catalyst prepared in example 1 and commercial Pt/C (20%) (0.1M HClO) 4 Solution), the half-wave potential dropped by 7mV and the commercial Pt/C electrode by 38 mV after 30000 cycles, indicating that the catalyst had good stability during the ORR reaction.
The fuel cell performance of the catalyst as the cathode was tested on a fuel cell test system. Prepared by electrostatic spraying method with area of 5.0 cm -2 Membrane Electrode Assembly (MEA). The catalyst (3 mg) was ultrasonically reacted with Nafion (20. Mu.L), isopropanol (144. Mu.L), and water (336. Mu.L) for 1h to form a homogeneous ink. The ink was then sprayed onto a Nafion 211 membrane at 70 ℃. Fuel cell testing was performed in a single cell using a commercial fuel cell testing system (Scribner 850e, cluster next energy limited). The MEA is sandwiched with sheetsBetween two graphite plates of the snakelike flow passage. The cell was operated at 80 ℃ and a backpressure of 150 kPa. Pure hydrogen and air/oxygen at a relative humidity of 100% are supplied to the anode and cathode at a gas flow rate of 500-1000 sccm. The fuel cell polarization curve was recorded using a potential step mode of 50 mV/point (each point held for 2 min). FIG. 5 (d) shows the data of the acid fuel cell tested on the catalyst material Pt-Zn/KB-1 prepared in example 1. As can be seen in fig. 5 (d): the peak power density of the catalyst Pt-Zn/KB-1 is 1449.48mW cm -2 Higher peak power density than commercial Pt/C (1149.95 mW cm) -2 ）。
In summary, it can be seen that: the novel fuel cell low-platinum alloy catalyst Pt-Zn/KB-1 material adjusts the electronic structure of the surface Pt through the addition of zinc and the existence of a high-index crystal face of an ultrathin platinum-rich surface skin, so that the catalytic activity is improved. The atoms at the steps, platforms and kinks of the high index nanocrystals can serve as additional catalytically active sites, facilitating catalysis. Namely, the invention manufactures high-index nano-crystals, and uniformly dispersed small-size Pt metal nano-particles (3-5 nm) are prepared by using atoms at steps, platforms and kinks as active sites. The reduction of the particle diameter enables the catalyst to expose more active surface beneficial to catalysis, so that the Pt-Zn/KB-1 catalyst shows higher half-wave potential in the ORR process and the half-wave potential is reduced by 7mV after circulating 30000 circles, which shows that the catalyst has high-efficiency catalysis and stability performance in the ORR reaction process. The peak power density of the assembled proton exchange membrane fuel cell is 1449.48mW cm -2 The performance is superior to that of the commercial Pt/C catalyst.
Claims (5)
1. The preparation method of the fuel cell platinum alloy catalyst is characterized by comprising the following steps:
1) Uniformly mixing benzyl alcohol and acetaldehyde to form a first mixed solution;
2) Adding acetylacetone platinum, hydrated acetylacetone zinc and polyvinylpyrrolidone into the first mixed solution, and uniformly mixing to form a second mixed solution;
3) Transferring the second mixed solution into a reaction kettle; sealing and heating the reaction kettle to 160-200 ℃, keeping the temperature for 8-10h, and naturally cooling to room temperature to obtain a third mixed solution;
4) Centrifuging the third mixed solution, washing with a mixed solution of cyclohexane and ethanol, and collecting the obtained product;
5) Washing the obtained product with glacial acetic acid, centrifugally collecting, washing with ethanol for several times, and drying to obtain Pt-Zn nanocrystalline; loading Pt-Zn nanocrystalline on Ketjen black to obtain the material;
the mass ratio of the acetylacetone platinum to the hydrated acetylacetone zinc to the polyvinylpyrrolidone is 1:1.2-1.3:13-18;
in the step 1), the volume ratio of benzyl alcohol to acetaldehyde is 1:0.5 to 2;
the Pt-Zn nanocrystalline is a concave Pt-Zn nanocube.
2. The method for preparing a platinum alloy catalyst for a fuel cell according to claim 1, wherein the heating from room temperature to 180 ℃ is performed within 30min in the step 3).
3. The method for preparing a platinum alloy catalyst for a fuel cell according to claim 1, wherein the volume ratio of cyclohexane to ethanol in the step 4) is 0.5 to 2:1.
4. a fuel cell platinum alloy catalyst prepared by the preparation method according to any one of claims 1 to 3.
5. Use of the fuel cell platinum alloy catalyst of claim 4 in a proton exchange membrane fuel cell.
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| CN113206259B (en) * | 2021-04-22 | 2023-04-11 | 华中科技大学 | Platinum-based intermetallic nanocrystalline with ordered structure, and preparation and application thereof |
| CN113422073B (en) * | 2021-06-23 | 2023-10-20 | 长春黄金研究院有限公司 | Preparation method of cobalt-modified carbon-supported superfine platinum nano alloy catalyst |
| CN113571713A (en) * | 2021-07-22 | 2021-10-29 | 山东能源集团有限公司 | PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell |
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