A noble metal-based alloy catalyst, a preparation method and application thereof

Abstract

The application provides a noble metal-based alloy catalyst and a preparation method and application thereof, and relates to the fields of catalyst preparation and electrocatalysis technology.The application comprises the following steps: mixing a carbon material and a phosphorus source by ball milling, roasting the dried solid, and obtaining a phosphorus-functionalized carrier; mixing the phosphorus-functionalized carrier, water and a noble metal salt, stirring, reducing and roasting the obtained solid product, and obtaining a noble metal seed; mixing the noble metal seed, water and a non-noble metal salt, stirring, and high-temperature roasting the obtained solid product, and obtaining a noble metal-based alloy catalyst.The catalyst prepared by the application has a noble metal content of only 10% of that of a commercial catalyst, and has catalytic performance and excellent stability which exceed those of a commercial platinum-carbon catalyst.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst preparation and electrocatalysis, in particular to a noble metal-based alloy catalyst and a preparation method and application thereof. BACKGROUND

[0002] Hydrogen energy, as a clean energy, plays an important role in the energy transformation in China. The use of renewable energy to electrolyze water to produce hydrogen helps to decarbonize the hydrogen production process. Among them, the proton exchange membrane electrolyzer (PEMEC) technology has high current density, fast response speed, small occupation, and can operate at low temperature, which is very suitable for coupling with renewable energy such as solar energy and wind energy, forming a dynamic, efficient and clean hydrogen production process, and has broad practical application potential. However, the commercial application of PEEMC still faces many problems. For example, as one of the most effective cathode catalysts for water electrolysis, platinum is scarce in resource reserves and expensive in price; under harsh electrochemical conditions, platinum nanoparticles will dissolve and agglomerate, resulting in performance degradation, so a higher platinum loading is often required to maintain hydrogen production efficiency; high loading, low activity, and low stability further increase the cost of PEM electrolysis of water, limiting the practical application of PEM electrolytic water chemical hydrogen production. Therefore, designing and developing high-efficiency low-platinum cathode catalysts is of great significance to accelerate the application and development of electrochemical hydrogen production.

[0003] Compared with traditional platinum-carbon catalysts, small-size platinum alloy catalysts can improve the optimization of platinum active sites and reduce the amount of platinum through the interaction of noble metals and non-noble metals, stress effect, ligand effect and geometric effect; at the same time, reducing the size of platinum particles to nanometer or sub-nanometer level can improve the atomic utilization rate. However, the alloy nanoparticles obtained by the current preparation method of platinum alloy catalysts are often large and uneven; moreover, the current preparation method has some process problems. For example, the preparation process of colloidal method is complex, the reaction steps are many, and it is difficult to remove the synthesis aid, which is not suitable for large-scale production. The use of precipitants in the precipitation method can easily cause local concentration to be too high, resulting in nanoparticle agglomeration problems. The impregnation method often needs a reduction step. The liquid phase reduction method is a method in which the reducing agent reduces the metal precursor while loading it onto the surface of the carrier. The catalyst obtained in this way has weak bonding force with the carrier, and the nanoparticle components are uneven, thereby affecting the catalytic activity and stability. The gas phase reduction method requires a higher temperature. During the high-temperature treatment process, sintering of nanoparticles is easy to occur, forming larger particles, which leads to a decrease in platinum atomic utilization and catalyst mass activity. Therefore, optimizing the preparation method of platinum alloy catalysts and developing ultra-stable high-dispersion small-size platinum alloy catalysts are of great significance to improve the catalytic activity and reduce the amount of noble metals. SUMMARY

[0004] In order to solve the above problems, the application provides a noble metal-based alloy catalyst and a preparation method and application thereof, the catalyst prepared by the application has a noble metal content of only 10% of commercial catalysts, and has catalytic performance and excellent stability beyond commercial platinum-carbon catalysts.

[0005] In order to achieve the above-mentioned purpose, the application provides the following technical scheme.

[0006] The application provides a preparation method of a noble metal-based alloy catalyst, comprising the following steps.

[0007] 1) carbon material and phosphorus source are ball-mixed, the dried solid is calcined to obtain a phosphorus-functionalized carrier;

[0008] 2) the phosphorus-functionalized carrier obtained in step 1) is mixed with water and a noble metal salt, and stirred, and the obtained solid product is subjected to reduction calcination to obtain a noble metal seed;

[0009] 3) the noble metal seed obtained in step 2) is mixed with water and a non-noble metal salt, and stirred, and the obtained solid product is subjected to high-temperature calcination to obtain a noble metal-based alloy catalyst.

[0010] Preferably, the phosphorus source in step 1) comprises phytic acid.

[0011] The mass ratio of the carbon material to the phosphorus source is 1:1-6.

[0012] The carbon material comprises XC-72, activated carbon, carbon nanotube, carbon fiber, graphene or mesoporous carbon.

[0013] Preferably, the calcination conditions in step 1) comprise a temperature of 300-500 DEG C and a time of 2 h.

[0014] The ball-mixing conditions comprise a time of 2-5 h and a rotation speed of 100-500 rpm.

[0015] Preferably, the noble metal salt in step 2) comprises chloroplatinic acid, potassium tetrachloroplatinate, platinum acetylacetone or iridium trichloride.

[0016] Preferably, the mass percentage content of the noble metal loaded on the phosphorus-functionalized carrier is 1-5%, and the mass ratio of the water to the phosphorus-functionalized carrier is 100-500:1.

[0017] Preferably, the reduction calcination conditions in step 2) comprise a temperature of 100-300 DEG C and a time of 1-3 h.

[0018] Preferably, the non-noble metal salt in step 3) comprises a nitrate or chloride salt of cobalt, iron, nickel, vanadium or chromium.

[0019] Preferably, the percentage content of the non-noble metal on the noble metal seed in the non-noble metal salt in step 3) is 5-10%, and the mass ratio of the water to the noble metal seed is 100-500:1.

[0020] Preferably, the high-temperature calcination in step 3) is performed under the following conditions: a temperature of 700-1000 DEG C and a time of 1-3 h.

[0021] The application also provides a noble metal-based alloy catalyst prepared by the preparation method.

[0022] The application also provides application of the noble metal-based alloy catalyst in hydrogen evolution from water electrolysis of a proton exchange membrane.

[0023] The application has the following beneficial effects:

[0024] 1. The application first uses a functionalized active carbon carrier with rich phosphorus functional groups to replace a conventional carbon carrier to prepare an ultra-small noble metal alloy nanoparticle catalyst material. The strong interaction between the phosphorus functional groups after functionalization and noble metal ions makes the metal ions uniformly dispersed on the carrier, effectively inhibits the agglomeration and growth of particles in the reduction process, and achieves high dispersion effect.

[0025] 2. The catalyst material of the application effectively solves the problems of catalyst falling off caused by insufficient contact and weak interaction force between the noble metal of the conventional catalyst and the carrier through the strong interaction between phosphorus and the ultra-small alloy nanoparticles. The size of the platinum-based alloy nanoparticles described in the examples of the application hardly changes before and after the large-current constant-current test, and has strong practical application value.

[0026] 3. The catalyst material of the application realizes the synergistic regulation of the electronic structure of the noble metal through alloying with non-noble metals, optimizes the internal electronic state distribution of the catalyst material, and greatly improves the electrocatalytic hydrogen evolution activity.

[0027] 4. The platinum-based alloy nanoparticles described in the examples of the application are all less than 3 nm, and some examples can even achieve sub-nanometer cluster degree. When used in the PEM water electrolysis hydrogen evolution reaction, the platinum-based alloy nanoparticles can greatly improve the atomic utilization rate and reaction activity, reduce the amount of noble metal, and reduce the cost of the catalyst.

[0028] 5. The preparation method of the application is simple and can realize large-scale production of carbon-loaded ultra-small platinum-based alloy catalysts. Meanwhile, the method has excellent synthesis universality and can be extended to the large-scale production and preparation of iridium ultra-small metal alloys. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to make the technical solutions in the embodiments of the present application or the prior art clearer, the accompanying drawings needed in the embodiments will be briefly introduced as follows.

[0030] Figure 1 Transmission electron microscopy image of small size platinum cobalt alloy nanocatalyst supported on phosphorus functionalized activated carbon support for Example 1.

[0031] Figure 2 Transmission electron microscopy image of small size platinum nickel alloy nanocatalyst supported on phosphorus functionalized activated carbon support for Example 3.

[0032] Figure 3 Transmission electron microscopy image of Example 3 and commercial platinum carbon catalyst after constant current stability test at 50 mA / cm 2

[0033] Figure 4 Transmission electron microscopy image of Example 3 after constant current stability test at 50 mA / cm 2

[0034] Figure 5 Transmission electron microscopy image of small size iridium iron alloy nanocatalyst supported on phosphorus functionalized activated carbon support for Example 4.

[0035] Figure 6 Transmission electron microscopy image of platinum nickel nanocatalyst supported on non-functionalized activated carbon support for Comparative Example 1.

[0036] Figure 7 Transmission electron microscopy image of platinum nanocatalyst supported on phosphorus functionalized activated carbon for Comparative Example 2. DETAILED DESCRIPTION

[0037] The present application provides a preparation method of a noble metal-based alloy catalyst, comprising the following steps:

[0038] 1) ball-milling mixing a carbon material with a phosphorus source, roasting the dried solid to obtain a phosphorus functionalized support;

[0039] 2) mixing and stirring the phosphorus functionalized support obtained in step 1) with water and a noble metal salt, and reducing and roasting the obtained solid product to obtain a noble metal seed;

[0040] 3) mixing and stirring the noble metal seed obtained in step 2) with water and a non-noble metal salt, and high-temperature roasting the obtained solid product to obtain a noble metal-based alloy catalyst.

[0041] ​​The carbon material is ball-mixed with a phosphorus source, and the dried solid is calcined to obtain a phosphorus-functionalized carrier. In the present application, the phosphorus source preferably includes phytic acid. In the present application, the mass ratio of the carbon material to the phosphorus source is preferably 1:1-6. In the present application, the carbon material includes preferably XC-72, activated carbon, carbon nanotubes, carbon fibers, graphene or mesoporous carbon. In the present application, the calcination conditions preferably include a temperature of 300-500 DEG C and a time of 2 h. In the present application, the ball-mixing conditions preferably include a time of 2-5 h and a rotation speed of 100-500 rpm. In the present application, the carbon material, the phosphorus source and a water-ethanol solution with a volume ratio of 1:5 are mixed before ball-mixing, wherein the concentration of the carbon material in the water-ethanol solution is 10 g / L. In the present application, the ball-mixed material is dried before calcination, and the drying temperature is preferably 60 DEG C.

[0042] The obtained phosphorus-functionalized carrier is mixed with water and a noble metal salt, and stirred to obtain a solid product, which is then reduced and calcined to obtain a noble metal seed. In the present application, the noble metal salt preferably includes chloroplatinic acid, potassium tetrachloroplatinate, platinum acetylacetone or iridium trichloride. In the present application, the mass percentage of the noble metal loaded on the phosphorus-functionalized carrier is 1-5%, and the mass ratio of the water to the phosphorus-functionalized carrier is 100-500:1. In the present application, the reduction and calcination conditions preferably include a temperature of 100-300 DEG C and a time of 1-3 h. In the present application, the stirring time is preferably 8 h. In the present application, the ball-mixed material is dried before reduction and calcination.

[0043] The obtained noble metal seed is mixed with water and a non-noble metal salt, and stirred to obtain a solid product, which is then high-temperature calcined to obtain a noble metal-based alloy catalyst. In the present application, the non-noble metal salt includes preferably a nitrate or chloride salt of a non-noble metal such as cobalt, iron, nickel, vanadium or chromium. In the present application, the mass percentage of the non-noble metal in the non-noble metal salt loaded on the noble metal seed is 5-10%, and the mass ratio of the water to the noble metal seed is 100-500:1. In the present application, the high-temperature calcination conditions preferably include a temperature of 700-1000 DEG C and a time of 1-3 h.

[0044] The present application also provides a noble metal-based alloy catalyst prepared by the preparation method described above, wherein the mass percentage of the noble metal in the noble metal-based alloy catalyst is 1-5%, and the particle size of the noble metal-based alloy is 1-3 nm.

[0045] The present application also provides an application of the noble metal-based alloy catalyst described above in the electrolytic hydrogen evolution of a proton exchange membrane.

[0046] In order to further illustrate the present application, the present application is described in detail below in conjunction with the examples, but they should not be construed as limiting the scope of the present application. Example 1

[0047] Take 2 g of activated carbon and 3 g of phytic acid solution with a mass percentage of 50% and mix with 200 ml of water-ethanol solution with a volume ratio of 1:5 for 3 h of ball milling at a speed of 250 rpm. The black slurry obtained is placed in a stainless steel tray and dried in an oven at 60°C. The solid mixture obtained is placed in a crucible and calcined in a muffle furnace at 500°C for 2 h. The calcined solid powder is washed thoroughly with water and dried to obtain the phosphorus functionalized support.

[0048] Take 1 g of the phosphorus functionalized support described above and disperse it in 500 ml of deionized water, then add 112 mg of potassium tetrachloroplatinate, stir thoroughly for 8 h, then separate by centrifugation or suction filtration and dry. The solid product obtained is reduced at 200°C for 2 h in a hydrogen-argon mixed gas atmosphere containing 5% hydrogen to produce ultra-small size platinum seed crystals. The platinum seed crystals obtained are further impregnated in a 500 ml solution of cobalt nitrate with a concentration of 1.1 g / L, then separated by centrifugation or filtration after thorough stirring, and dried to obtain a solid product. Finally, the solid product obtained is reduced at 700°C for 3 h in a hydrogen-argon mixed gas atmosphere containing 5% hydrogen to obtain a supported small size platinum-cobalt alloy catalyst. The final mass percentage of noble metal platinum is 3.1% and the mass percentage of cobalt is 0.3%.

[0049] Figure 1 The transmission electron microscopy (TEM) image of the small size platinum-cobalt alloy catalyst obtained is shown in Figure 2. Figure 1 As can be seen, the platinum-cobalt alloy nanoparticles are uniformly distributed on the carbon support, with a particle size of about 2 nm.

[0050] The platinum-cobalt alloy catalyst of the present example is used as a water electrolysis hydrogen production catalyst for electrochemical testing. The working electrode is prepared as follows: take 5 mg of the catalyst and add it to a solution containing 0.2 ml of isopropyl alcohol, 0.25 ml of water, and 0.05 ml of 5% Nafion, ultrasonically disperse to form an ink slurry of 10 mg / ml. Take 3 μl and drop it on a 3 mm glassy carbon electrode, and dry. The reference electrode is a saturated Ag / AgCl electrode, and the counter electrode is a smooth platinum sheet. The electrolyte is a 0.5 mol / L sulfuric acid solution that has been deoxygenated with nitrogen. The electrochemical activity and stability of the catalyst are compared by linear sweep voltammetry and constant current electrolysis. At the same time, a 20% commercial Pt / C catalyst is used for comparison, and the electrochemical activity results are shown in Table 1. Example 2

[0051] The phosphorus functionalized support and small size platinum seed crystals are prepared in the same way as in Example 1.

[0052] Take 1 g of ultra-small size platinum metal seed and disperse it in 500 ml of deionized water. During stirring, add 802 mg of ferric nitrate, and fully stir and soak for 12 h. Then separate by centrifugation or filtration, and dry to obtain a solid product. Finally, reduce the obtained solid product at 800°C for 3 h in a hydrogen atmosphere containing 5% hydrogen and argon to obtain a supported small-size platinum-iron alloy catalyst. The final mass percentage of noble metal platinum is 2.9%, and the mass percentage of iron is 0.9%.

[0053] The platinum-iron alloy catalyst of the present example was subjected to electrochemical testing as a water electrolysis hydrogen production catalyst, and the electrochemical activity results are shown in Table 1. Example 3

[0054] The same method as in Example 1 was used to prepare a phosphorus functionalized carrier and small-size platinum metal seed.

[0055] Take 1 g of ultra-small size platinum metal seed and disperse it in 500 ml of deionized water. During stirring, add 262 mg of nickel nitrate, and fully stir and soak for 12 h. Then separate by centrifugation or filtration, and dry to obtain a solid product. Finally, reduce the obtained solid product at 800°C for 3 h in a hydrogen atmosphere containing 5% hydrogen and argon to obtain a supported small-size platinum-nickel alloy catalyst. The final mass percentage of noble metal platinum is 2.5%, and the mass percentage of nickel is 0.5%.

[0056] Figure 2 A TEM image of the small-size platinum-nickel alloy catalyst obtained is shown in Figure 2. Figure 2 It can be seen that the platinum-nickel alloy nanoparticles are uniformly distributed on the carbon carrier, and the particle size is about 1.9 nm.

[0057] The platinum-nickel alloy catalyst of the present example was subjected to electrochemical testing as a water electrolysis hydrogen production catalyst, and the electrochemical activity results are shown in Table 1. The platinum-nickel alloy catalyst was subjected to large-current constant-current electrolysis as a water electrolysis hydrogen evolution catalyst, and the results are shown in Figure 3. Figure 3 .

[0058] The platinum-nickel alloy catalyst was subjected to electron microscopy characterization after constant-current electrolysis for 100 h, and the results are shown in Figure 4. Figure 4 . Example 4

[0059] Take 2 g of activated carbon and 6 g of a phytic acid solution with a mass concentration of 50% and mix with 200 ml of a water-ethanol solution with a volume ratio of 1:5 by ball milling at a speed of 250 rpm for 3 h. Place the obtained black slurry in a stainless steel tray and dry in an oven at 60°C. Place the obtained solid mixture in a crucible and calcine in a muffle furnace in an air atmosphere at 300°C for 2 h. Wash the calcined solid powder with water, and dry to obtain a phosphorus functionalized carrier.

[0060] The 1 g of the phosphorus functionalized support was dispersed in 500 ml of deionized water, and 173 mg of iridium salt was added for stirring impregnation for 8 h. Then, the solid product was separated by centrifugation or suction filtration and dried. The obtained solid product was calcined at 250 °C for 2 h in a hydrogen atmosphere containing 5% of hydrogen in argon to obtain ultra-small size iridium metal seeds. The obtained iridium seeds were further impregnated in 300 ml of 1.2 g / L ferric nitrate solution for 12 h, and then separated by centrifugation or filtration after sufficient stirring. The obtained solid product was reduced at 800 °C for 3 h in a hydrogen atmosphere containing 5% of hydrogen in argon to obtain a supported small size iridium-iron alloy catalyst. The obtained sample had a mass percentage of 2.6% of iridium and about 0.8% of iron.

[0061] Figure 5 The transmission electron microscopy (TEM) image of the obtained small size iridium-iron alloy catalyst is shown in Figure 2. Figure 5 It can be seen that the iridium-iron alloy nanoparticles are uniformly distributed on the carbon support, and the particle size is 1-3 nm.

[0062] The iridium-iron alloy catalyst of the present example was used as a water electrolysis hydrogen production catalyst for electrochemical test, and the electrochemical activity results are shown in Table 1. Example 5

[0063] The phosphorus functionalized support and ultra-small size iridium metal seeds were prepared by the same method as in Example 4.

[0064] The 1 g of the ultra-small size iridium metal seeds was dispersed in 500 ml of deionized water, and 162 mg of vanadium chloride was added for stirring impregnation for 12 h. Then, the solid product was separated by centrifugation or suction filtration and dried. The obtained solid product was reduced at 900 °C for 3 h in a hydrogen atmosphere containing 5% of hydrogen in argon to obtain a supported small size iridium-vanadium alloy catalyst. The obtained sample had a mass percentage of 2.8% of iridium and about 0.6% of vanadium.

[0065] The iridium-vanadium alloy catalyst of the present example was used as a water electrolysis hydrogen production catalyst for electrochemical test, and the electrochemical activity results are shown in Table 1. Example 6

[0066] The phosphorus functionalized support and ultra-small size iridium metal seeds were prepared by the same method as in Example 4.

[0067] The 1 g of the ultra-small size iridium metal seeds was dispersed in 500 ml of deionized water, and 161 mg of chromium chloride was added for stirring impregnation for 12 h. Then, the solid product was separated by centrifugation or suction filtration and dried. The obtained solid product was reduced at 800 °C for 3 h in a hydrogen atmosphere containing 5% of hydrogen in argon to obtain a supported small size iridium-chromium alloy catalyst. The obtained sample had a mass percentage of 2.6% of iridium and 0.6% of chromium.

[0068] The iridium-chromium alloy catalyst of the present example was electrochemically tested as a water electrolysis hydrogen production catalyst, and the electrochemical activity results are shown in Table 1.

[0069] Comparative Example 1

[0070] A 1 g of activated carbon was dispersed in 500 ml of deionized water, and then 112 mg of potassium tetrachloroplatinate was added. After stirring for 8 h, the mixture was separated by centrifugation or suction filtration, and the solid product was dried. The obtained solid product was reduced at 200 °C for 2 h in a hydrogen atmosphere containing 5% hydrogen in argon. The reduced sample was then immersed in a nickel salt solution, and after stirring, the mixture was separated by centrifugation or suction filtration, and the solid product was dried. Finally, the obtained solid product was reduced at 800 °C for 2 h in a hydrogen atmosphere containing 5% hydrogen in argon to obtain an activated carbon supported platinum-nickel alloy catalyst. The mass percentage of the noble metal platinum was 3.2%, and the mass percentage of nickel was 0.8%.

[0071] Figure 6 The transmission electron microscopy image of the obtained activated carbon supported platinum-nickel nanoparticle catalyst is shown in Figure 1. Figure 6 It can be seen that the platinum-nickel nanoparticles are unevenly distributed on the surface of the non-functionalized activated carbon, and the particle size is large and uneven, ranging from 2-7 nm.

[0072] The non-functionalized activated carbon supported platinum nanoparticle catalyst of the present example was electrochemically tested as a water electrolysis hydrogen production catalyst, and the electrochemical activity results are shown in Table 1.

[0073] Comparative Example 2

[0074] The phosphorus functionalized support and small size platinum seed crystals were prepared by the same method as in Example 1. The obtained platinum seed crystals were reduced at 800 °C for 3 h in a hydrogen atmosphere containing 5% hydrogen in argon to obtain a phosphorus functionalized activated carbon supported platinum nanoparticle catalyst.

[0075] Figure 7 The transmission electron microscopy image of the obtained phosphorus functionalized activated carbon supported platinum nanoparticle catalyst is shown in Figure 2. Figure 7 It can be seen that the platinum nanoparticles are uniformly distributed, and the particle size is about 1.7 nm.

[0076] The functionalized activated carbon supported platinum nanoparticle catalyst of the present example was electrochemically tested as a water electrolysis hydrogen production catalyst, and the electrochemical activity results are shown in Table 1.

[0077] Table 1 Water electrolysis hydrogen production activity test of the catalysts of Examples 1-6 and Comparative Examples 1-2 and commercial platinum-carbon catalyst

[0078] Serial number 10 mA / cm 2 time overpotential (mV) 100 mA / cm 2 time potential (mV) Example 1 28 97 Example 2 23 91 Example 3 17 62 Example 4 26 82 Example 5 30 99 Example 6 27 101 Comparative Example 1 31 108 Comparative Example 2 30 101 Commercial platinum carbon 35 123

[0079] Table 1 shows the water electrolysis hydrogen production activity of the catalysts of Examples 1-6, Comparative Examples 1-2 and commercial platinum-carbon catalyst at 10 mA / cm 2and 100 mA / cm 2 The overpotential comparison under the current density. It can be seen from the figure that the electrocatalytic hydrogen evolution activity of the phosphorus functionalized activated carbon supported platinum-based alloy catalysts of examples 1-3 is much higher than that of the non-functionalized activated carbon supported platinum-based alloy catalyst; compared with comparative example 2, the doping of non-noble metal also helps to improve the electrocatalytic activity. Examples 4-6 show that the preparation method is also suitable for the preparation and synthesis of other noble metal alloys.

[0080] The phosphorus functionalized activated carbon supported platinum alloy electrocatalyst material obtained by the present application Figure 3 It can be seen that the phosphorus functionalized activated carbon supported small size platinum alloy electrocatalyst material obtained by the present application exhibits excellent stability under large current constant current electrolysis conditions.

[0081] The phosphorus functionalized activated carbon supported platinum alloy electrocatalyst material obtained by the present application Figure 4 It can be seen that after long time large current constant current electrolysis, the platinum alloy nanoparticles are still uniformly distributed on the phosphorus functionalized carbon carrier, and the particle size is about 2 nm. Compared with the original nanoparticle size, the size is almost unchanged, which exhibits strong practical application value.

[0082] Although the above examples make a detailed description of the present application, it is only a part of the embodiments of the present application, but not all the embodiments, and people can also obtain other embodiments according to the present embodiments without creativity, which all belong to the protection scope of the present application.

Claims

1. A method for preparing a noble metal-based alloy catalyst, characterized by, For the following steps: Take 2 g of activated carbon and 3 g of phytic acid solution with a mass percentage of 50% and mix with 200 ml of water-ethanol solution with a volume ratio of 1:5 for 3 h ball milling at a speed of 250 rpm; place the obtained black slurry in a stainless steel tray and dry in an oven at 60°C; place the obtained solid mixture in a crucible and calcine in a muffle furnace at 500°C for 2 h; wash the calcined solid powder with water and dry to obtain a phosphorus functionalized carrier; Take 1 g of the above phosphorus functionalized carrier and disperse in 500 ml of deionized water, then add 112 mg of potassium tetrachloroplatinate, stir for 8 h, then centrifuge or filter to separate, and dry; reduce the obtained solid product in a hydrogen atmosphere containing 5% hydrogen in hydrogen-argon mixed gas at 200°C for 2 h to obtain ultra-small size platinum seed crystals; Take 1 g of ultra-small size platinum seed crystals and disperse in 500 ml of deionized water, then add 262 mg of nickel nitrate during stirring, and immerse for 12 h, then centrifuge or filter to separate, and dry to obtain a solid product; finally, reduce the obtained solid product in a hydrogen atmosphere containing 5% hydrogen in hydrogen-argon mixed gas at 800°C for 3 h to obtain a supported small size platinum-nickel alloy catalyst; the mass percentage of noble metal platinum is 2.5%, and the mass percentage of nickel is 0.5%.

2. A noble metal-based alloy catalyst prepared by the preparation method of claim 1, wherein the mass percentage of noble metal in the noble metal-based alloy catalyst is 2.5%, and the particle size of the noble metal-based alloy is 1.9 nm.

3. Use of the noble metal-based alloy catalyst of claim 2 in the electrolysis of water to produce hydrogen by a proton exchange membrane.

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