A noble metal-rare earth alloy nanocluster catalyst, a preparation method and application thereof

Abstract

The application provides a noble metal-rare earth alloy nanocluster catalyst and a preparation method and application thereof, and relates to the field of catalysts and preparation technologies thereof. The application comprises the following steps: mixing, ball-milling, and calcining carbon materials, a nitrogen source, and a phosphorus source to obtain a nitrogen-phosphorus functionalized activated carbon carrier; mixing and stirring the nitrogen-phosphorus functionalized activated carbon carrier with water and a rare earth salt, drying the obtained solid, and high-temperature calcining to obtain a composite carrier; mixing and stirring the composite carrier with water and a noble metal salt, drying the obtained solid, and reduction calcining to obtain a noble metal-rare earth alloy nanocluster catalyst. The application solves the problems of high cost, low electrolysis efficiency, poor stability, and the like of the existing catalysts for proton exchange membrane water electrolysis.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalysts and their preparation techniques, in particular to a noble metal-rare earth alloy nanocluster catalyst and a preparation method and application thereof. BACKGROUND

[0002] Renewable energy is an important development direction of human society. However, renewable energy is intermittent and cannot output electric energy stably and continuously for a long time, resulting in a large amount of waste of green energy. Coupling renewable energy with water electrolysis devices can convert renewable energy with large fluctuations into hydrogen energy which is easy to store and transport, and then widely applied to the fields of industry, transportation, construction, power and the like. Proton exchange membrane electrolysis cell (PEMEC) uses proton exchange membrane as electrolyte and pure water as reactant to produce high-purity hydrogen. It has the advantages of high current density, fast response speed and high gas purity, and is extremely suitable for coupling with renewable energy to convert electric energy into hydrogen energy for efficient storage. The performance of the electrode catalyst of the proton exchange membrane electrolysis cell determines the electrolysis efficiency, and how to improve the activity and stability of the catalyst is one of the focuses of academic research and industrial application.

[0003] Increasing the loading of noble metal catalysts is a method to improve water electrolysis performance. The cathode catalyst usually uses activated carbon supported platinum nanoparticle catalyst with a noble metal content of 40%-60%, and the size of the platinum nanoparticle is about 5nm. However, due to the weak interaction between platinum nanoparticles and carbon carriers, under high loading conditions, noble metal platinum nanoparticles are very easy to agglomerate, resulting in degradation of electrochemical activity and stability. In addition, platinum resources are limited and costly, and too high noble metal loading will also reduce the atomic utilization rate of noble metals, which is not conducive to its large-scale application in PEM electrolysis cells. Therefore, developing a low-platinum hydrogen production catalyst with high activity and high stability is of great significance to accelerate the commercialization of PEM water electrolysis technology. SUMMARY

[0004] In order to solve the above problems, the present application provides a noble metal-rare earth alloy nanocluster catalyst and a preparation method and application thereof, which solves the problems of high cost, low electrolysis efficiency and poor stability of the existing proton exchange membrane water electrolysis catalyst.

[0005] In order to achieve the above purpose, the present application provides the following technical solutions:

[0006] The present application provides a preparation method of a noble metal-rare earth alloy nanocluster catalyst, comprising the following steps:

[0007] 1) Ball-milling, mixing and calcining carbon materials, nitrogen sources and phosphorus sources to obtain a nitrogen and phosphorus functionalized activated carbon carrier;

[0008] 2) mixing the nitrogen-phosphorus functionalized active carbon carrier obtained in step 1) with water, a rare earth salt, stirring, drying the obtained solid and then high-temperature calcining to obtain a composite carrier;

[0009] 3) mixing the composite carrier obtained in step 2) with water, a noble metal salt, stirring, drying the obtained solid and then reduction calcining to obtain a noble metal-rare earth alloy nanocluster catalyst.

[0010] Preferably, the carbon material in step 1) comprises activated carbon, carbon nanotubes, graphene or mesoporous carbon;

[0011] The nitrogen source comprises urea, and the phosphorus source comprises a phytic acid solution with a mass percentage of 50%;

[0012] The mass ratio of the carbon material to the nitrogen source and the phosphorus source is 5:1:6.

[0013] Preferably, the ball-milling mixing condition in step 1) comprises a time of 1-3 h and a rotation speed of 100-600 rpm.

[0014] The calcining condition comprises a temperature of 800-1000℃ and a time of 2 h.

[0015] Preferably, the rare earth salt in step 2) comprises one or more of cerium nitrate, lanthanum nitrate, neodymium nitrate and praseodymium nitrate.

[0016] Preferably, the loading percentage of the rare earth element on the nitrogen-phosphorus functionalized active carbon carrier is 5-20%.

[0017] Preferably, the high-temperature calcining condition in step 2) comprises a temperature of 600-900℃ and a time of 1-3 h.

[0018] Preferably, the noble metal salt in step 3) comprises one or more of platinum acetylacetonate, potassium tetrachloroplatinate, chloroplatinic acid, iridium trichloride and iridium acetylacetonate.

[0019] The loading percentage of the noble metal on the composite carrier is 2-10%.

[0020] Preferably, the reduction calcining condition in step 3) comprises a temperature of 500-800℃ and a time of 1-3 h.

[0021] The present application also provides a noble metal-rare earth alloy nanocluster catalyst prepared by the preparation method described in the above technical solution, wherein the mass percentage of the noble metal in the noble metal-rare earth alloy nanocluster catalyst is 2.1%.

[0022] The particle size of the noble metal-rare earth alloy nanocluster catalyst is 1.3-2.5 nm.

[0023] The application further provides application of the noble metal-rare earth alloy nanocluster catalyst in the above technical solution in hydrogen evolution of a proton exchange membrane electrolysis cell.

[0024] The application has the following beneficial effects:

[0025] 1. The application first synthesizes a noble metal-rare earth nanocluster loaded on a heteroatom functionalized active carbon composite rare earth phosphate as a composite carrier and applied in a proton exchange membrane electrolysis cell. The application realizes high dispersion of ultra-small noble metal-rare earth alloy nanoclusters through surface confinement of the functionalized carbon carrier and spatial confinement of the rare earth phosphate nanoparticles.

[0026] 2. The catalyst material of the application has the characteristics of ultra-small size, which can fully expose low coordination and high activity metal sites; at the same time, the rare earth metal is beneficial to the adjustment of the electronic structure of the noble metal, and improves the intrinsic reaction activity of the metal.

[0027] 3. The noble metal-rare earth nanocluster of the application has a strong interaction with the phosphate nanoparticles and the functionalized carbon carrier, which can effectively inhibit the problem of catalyst falling off and agglomeration under reaction conditions. The catalyst described in the examples of the application has almost no change in size after being applied in a proton exchange membrane cathode catalyst in a large current constant current test.

[0028] 4. The catalyst of the application exhibits better hydrogen evolution reaction activity and stability than commercial noble metal catalysts under lower noble metal loading conditions, and is suitable for industrialized water electrolysis hydrogen production. The catalyst preparation method has a simple process, simple raw materials, strong universality, and can realize the large-scale production of various ultra-small noble metal-rare earth alloys. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the drawings needed to be used in the embodiments will be briefly introduced as follows.

[0030] Figure 1 The transmission electron microscope image of the nitrogen-phosphorus functionalized active carbon carrier loaded cerium phosphate nanoparticles of Example 1.

[0031] Figure 2 The composite carrier loaded ultra-small size platinum-cerium alloy catalyst obtained by amplification preparation of Example 1.

[0032] Figure 3 The transmission electron microscope image of the composite carrier loaded ultra-small size platinum-cerium alloy catalyst of Example 1.

[0033] Figure 4 The spherical aberration correction transmission electron microscope image of the composite carrier loaded ultra-small size platinum-cerium alloy catalyst of Example 1.

[0034] Figure 5 Stability test results of PEM membrane electrode assembled with commercial platinum carbon catalyst and Example 1 respectively under constant current 1 A / cm 2

[0035] Figure 6 Transmission electron microscopy image of Example 1 after constant current stability test at 1 A / cm 2

[0036] Figure 7 Transmission electron microscopy image of commercial platinum carbon catalyst after constant current stability test at 1 A / cm 2

[0037] Figure 8 Transmission electron microscopy image of Example 4 of ultra-small size platinum-praseodymium alloy catalyst supported on composite carrier.

[0038] Figure 9 Transmission electron microscopy image of Example 5 of ultra-small size iridium-cerium alloy catalyst supported on composite carrier.

[0039] Figure 10 Transmission electron microscopy image of Example 1 of platinum nanocatalyst supported on nitrogen and phosphorus functionalized activated carbon carrier. DETAILED DESCRIPTION

[0040] A preparation method of a noble metal-rare earth alloy nanocluster catalyst, characterized in that the method comprises the following steps:

[0041] 1) mixing, ball-milling and calcining a carbon material, a nitrogen source and a phosphorus source to obtain a nitrogen and phosphorus functionalized activated carbon carrier;

[0042] 2) mixing and stirring the nitrogen and phosphorus functionalized activated carbon carrier obtained in step 1) with water and a rare earth salt, drying the obtained solid and then high-temperature calcining to obtain a composite carrier;

[0043] 3) mixing and stirring the composite carrier obtained in step 2) with water and a noble metal salt, drying the obtained solid and then reduction calcining to obtain a noble metal-rare earth alloy nanocluster catalyst.

[0044] ​​​The carbon material, the nitrogen source and the phosphorus source are ball-milled, and then are calcined to obtain a nitrogen-phosphorus functionalized activated carbon carrier.In the application, the carbon material preferably includes activated carbon, carbon nanotube, graphene or mesoporous carbon.In the application, the nitrogen source preferably includes urea, and the phosphorus source preferably includes a phytic acid solution with a mass percentage of 50%.In the application, the mass ratio of the carbon material to the nitrogen source and the phosphorus source is preferably 5:1:6.In the application, the calcination is preferably carried out in an inert atmosphere.The carbon material, the nitrogen source, the phosphorus source and a water-ethanol solution with a volume ratio of 1:5 are mixed, and then are ball-milled, wherein the concentration of the carbon material in the water-ethanol solution is 20 g / L.In the application, the ball-milling conditions preferably include a time of 1-3 h and a rotating speed of 100-600 rpm.The ball-milled material is preferably dried and then is calcined.In the application, the calcination conditions preferably include a temperature of 800-1000 DEG C and a time of 2 h.

[0045] The nitrogen-phosphorus functionalized activated carbon carrier, water and a rare earth salt are mixed and stirred, and then the obtained solid is dried and is subjected to high-temperature calcination to obtain a composite carrier.In the application, the rare earth salt preferably includes one or more of cerium nitrate, lanthanum nitrate, neodymium nitrate and praseodymium nitrate.In the application, the loading percentage of the rare earth element on the nitrogen-phosphorus functionalized activated carbon carrier is 5-20%.In the application, the high-temperature calcination conditions preferably include a temperature of 600-900 DEG C and a time of 1-3 h.In the application, the stirring time is preferably 8-12 h.In the application, the high-temperature calcination is preferably carried out in a hydrogen-argon mixed gas with a hydrogen content of 5%.

[0046] The composite carrier, water and a noble metal salt are mixed and stirred, and then the obtained solid is dried and is subjected to reduction calcination to obtain a noble metal-rare earth alloy nanocluster catalyst.In the application, the noble metal salt preferably includes one or more of platinum acetylacetate, potassium tetrachloroplatinate, chloroplatinic acid, iridium trichloride and iridium acetylacetate.In the application, the loading percentage of the noble metal on the composite carrier is 2-10%.In the application, the reduction calcination conditions preferably include a temperature of 500-800 DEG C and a time of 1-3 h.In the application, the stirring time is preferably 8 h.

[0047] The application also provides a noble metal-rare earth alloy nanocluster catalyst prepared by the preparation method.

[0048] The application also provides application of the noble metal-rare earth alloy nanocluster catalyst in proton exchange membrane electrolytic water hydrogen evolution.

[0049] In order to further illustrate the present application, the present application is described in detail below in conjunction with examples, but they should not be understood as limiting the scope of the present application.

[0050] Example 1

[0051] 5 g of activated carbon, 1 g of urea and 6 g of phytic acid solution were weighed and mixed with 250 ml of water-alcohol solution with a volume ratio of 1:5 for 3 h of ball milling at a rotation speed of 250 rpm. The obtained black slurry was placed in a stainless steel tray and dried in an oven at 60°C. The obtained solid mixture was placed in a tube furnace and calcined at 800°C for 2 h under an argon atmosphere to obtain a nitrogen-phosphorus functionalized activated carbon support.

[0052] 1 g of the above-mentioned nitrogen-phosphorus functionalized activated carbon support was weighed and dispersed in 350 ml of deionized water, and 345 mg of cerium nitrate was added, and stirring was continued for 8 h. The solid product was separated by centrifugation or suction filtration device, and after sufficient drying, it was calcined at 800°C for 3 h under a hydrogen-argon mixed gas to obtain a composite support. The transmission electron microscopy (TEM) image of the obtained product is shown in Figure 1 From the figure, it can be seen that the cerium phosphate nanoparticles are uniformly dispersed on the surface of the functionalized support, and the average size is about 7.5 nm.

[0053] 1 g of the above-mentioned composite support was dispersed in 300 ml of deionized water, and then 112 mg of potassium tetrachloroplatinate was added, and after stirring for 8 h, it was separated by centrifugation or suction filtration and dried. The obtained solid powder was calcined at 700°C for 2 h under a hydrogen-argon mixed gas atmosphere with a hydrogen content of 5% to obtain a composite support loaded ultra-small size platinum-cerium alloy catalyst of the present application, wherein the mass percentage of platinum in the catalyst is 2.1%, and the mass percentage of cerium is 0.2%. As shown in Figure 2 , by further enlarging the amount of material, a macroscopic catalyst can be obtained. The transmission electron microscopy (TEM) image of the prepared catalyst is shown in Figure 3 It can be seen that the platinum-cerium alloy nanoclusters are uniformly distributed on the composite support, and the average size of the clusters is 1.3 nm. From the high-resolution transmission electron microscopy (HRTEM) image of the catalyst in Figure 4 , the lattice spacing of the larger size nanoparticles can be determined to be 0.3 nm, corresponding to the (101) crystal plane of CePO4, and the ultra-small nanoclusters on the surface of the cerium phosphate and functionalized carbon support are platinum-cerium alloy.

[0054] 4 mg of the above catalyst was weighed and added to a mixture of 0.18 ml isopropanol, 0.2 ml water, and 0.02 ml 5% Nafion solution. The mixture was ultrasonically dispersed to obtain a 10 mg / ml ink slurry. 3 μl of this slurry was dropped onto a 3 mm glassy carbon electrode and dried to obtain the working electrode. Using a saturated Ag / AgCl electrode as the reference electrode and a smooth platinum sheet as the counter electrode, electrochemical tests were performed in a 0.5 mol / L sulfuric acid solution deoxygenated under nitrogen. The performance was compared with that of a 20% commercial platinum-carbon catalyst. The electrochemical activity results are shown in Table 1.

[0055] The above-mentioned catalyst and iridium oxide were used as the cathode and anode catalysts, respectively, in a PEM electrolyzer to prepare an active area of ​​5 cm². 2 The membrane electrode was subjected to constant current electrolysis in an electrolytic cell at 80°C. Similarly, with 20% commercial platinum-carbon as a control catalyst, the results were as follows: Figure 5 The comparison shows that, compared with a 20% commercial platinum-carbon catalyst, the ultra-small platinum-cerium alloy catalyst supported on the composite support of this invention exhibits superior electrocatalytic water splitting performance and remains stable after a circuit restart. Furthermore, and most importantly, the platinum loading in the membrane electrode can be reduced by 5 times, demonstrating significant potential for cost reduction. (At 2 A / cm) 2 Transmission electron microscopy (TEM) images of the ultra-small platinum-cerium alloy catalyst supported on the composite support after 100 hours of constant current electrolysis are shown below. Figure 6 As shown, cerium phosphate nanoparticles and platinum-cerium alloy nanoclusters are still uniformly distributed on the carbon-supported surface, with an average cluster size of 1.7 nm. From... Figure 7 It can be observed that 20% commercial platinum carbon exhibits significant aggregation after constant current electrolysis testing.

[0056] Example 2

[0057] The nitrogen and phosphorus functionalized activated carbon support was prepared using the same method as in Example 1. 1 g of the functionalized activated carbon support was weighed and dispersed in 350 ml of deionized water. 346 mg of lanthanum nitrate was added, and the mixture was stirred continuously for 8-12 hours. Afterward, it was separated by centrifugation or vacuum filtration. After thorough drying, it was calcined at 800 °C for 2 hours in a tube furnace under a hydrogen-argon mixed atmosphere to obtain the composite support.

[0058] The above-mentioned 1g composite support was dispersed in 300ml of deionized water, and then 112mg of potassium tetrachloroplatinate was added. After stirring thoroughly for 8 hours, the mixture was separated by centrifugation or vacuum filtration and dried. The resulting solid powder was calcined at 800℃ for 2 hours under a hydrogen-argon mixture to obtain the ultra-small platinum-lanthanum alloy catalyst supported on the composite support of the present invention. The mass percentage of platinum in the catalyst was 2.3%, and the mass percentage of lanthanum was 0.3%.

[0059] The platinum-lanthanum alloy catalyst of the present example was electrochemically tested as a hydrogen production catalyst for water electrolysis in a three-electrode system. The working electrode preparation process was consistent with Example 1, and the electrochemical activity results are shown in Table 1.

[0060] Example 3

[0061] A nitrogen-phosphorus functionalized activated carbon carrier was prepared by the same method as in Example 1. 1 g of the functionalized activated carbon carrier was dispersed in 350 ml of deionized water, and 160 mg of neodymium nitrate was added. After continuous stirring for 8-12 h, centrifugation or suction filtration was performed for separation. After sufficient drying, the composite carrier was obtained by calcination under a hydrogen-argon mixed gas at 800°C for 2 h in a tube furnace.

[0062] 1 g of the above composite carrier was dispersed in deionized water, and then 112 mg of potassium tetrachloroplatinate was added. After sufficient stirring for 8 h, centrifugation or suction filtration was performed for separation, and drying treatment was performed. The obtained solid powder was reduced and calcined at 700°C under a hydrogen-argon mixed gas for 2 h to obtain a composite carrier supported ultra-small size platinum-neodymium alloy catalyst of the present application. The mass percentage of platinum in the catalyst was 2.2%, and the mass percentage of neodymium was 0.2%.

[0063] The platinum-neodymium alloy catalyst of the present example was electrochemically tested as a hydrogen production catalyst for water electrolysis in a three-electrode system. The working electrode preparation process was consistent with Example 1, and the electrochemical activity results are shown in Table 1.

[0064] Example 4

[0065] A nitrogen-phosphorus functionalized activated carbon carrier was prepared by the same method as in Example 1. 1 g of the functionalized activated carbon carrier was dispersed in deionized water, and 162 mg of praseodymium nitrate was added. After continuous stirring for 8-12 h, centrifugation or suction filtration was performed for separation. After sufficient drying, the composite carrier was obtained by calcination under a hydrogen-argon mixed gas at 800°C for 1 h in a tube furnace.

[0066] 1 g of the above composite carrier was dispersed in 300 ml of deionized water, and then 112 mg of potassium tetrachloroplatinate was added. After sufficient stirring for 8 h, centrifugation or suction filtration was performed for separation, and drying treatment was performed. The obtained solid powder was reduced and calcined at 800°C under a hydrogen-argon mixed gas for 2 h to obtain a composite carrier supported ultra-small size platinum-praseodymium alloy catalyst of the present application. The mass percentage of platinum in the catalyst was 2.1%, and the mass percentage of praseodymium was 0.2%. The transmission electron microscope (TEM) image of the prepared catalyst is shown in FIG. 2, and it can be seen that the platinum-praseodymium alloy nanoclusters are uniformly distributed on the composite carrier, and the average size of the nanoclusters is 1.7 nm. Figure 8

[0067] The platinum-praseodymium alloy catalyst of the present example was electrochemically tested as a hydrogen production catalyst for water electrolysis in a three-electrode system. The working electrode preparation process was consistent with Example 1, and the electrochemical activity results are shown in Table 1. ​

[0068] Example 5

[0069] The nitrogen and phosphorus functionalized activated carbon support and the composite support loaded with cerium phosphate were prepared by the same method as in Example 1.

[0070] The composite support was dispersed in 350 ml of deionized water, and then 108 mg of iridium trichloride was added. After stirring for 8 h, the product was separated by centrifugation or suction filtration and dried. The obtained solid powder was reduced and calcined at 900 °C under a hydrogen-argon mixed gas for 2 h to obtain the composite support loaded with an ultra-small size iridium-cerium alloy catalyst of the present application. The mass percentage of iridium in the catalyst was 2.5%, and the mass percentage of cerium was 0.2%. The transmission electron microscopy (TEM) image of the prepared catalyst is shown in FIG. 2, and it can be seen that the iridium-cerium alloy nanoclusters are uniformly distributed on the composite support, and the average size of the nanoclusters is 1.6 nm. Figure 9

[0071] The iridium-cerium alloy catalyst of the present example was used as a water electrolysis hydrogen production catalyst in a three-electrode system for electrochemical testing, and the results are shown in Table 1.

[0072] Comparative Example 1

[0073] The nitrogen and phosphorus functionalized activated carbon support was prepared by the same method as in Example 1.

[0074] The nitrogen and phosphorus functionalized activated carbon support was dispersed in 350 ml of deionized water, and then 112 mg of potassium tetrachloroplatinate was added. After stirring for 8 h, the product was separated by centrifugation or suction filtration and dried. The obtained solid powder was reduced and calcined at 700 °C under a hydrogen-argon mixed gas for 2 h to obtain platinum nanoclusters supported on the nitrogen and phosphorus functionalized activated carbon. The mass percentage of platinum in the catalyst was 2.6%. The transmission electron microscopy (TEM) image of the prepared catalyst is shown in FIG. 3, and it can be seen that the average size of the platinum nanoclusters is 1.8 nm. Figure 10

[0075] The nitrogen and phosphorus functionalized activated carbon support was used as a water electrolysis hydrogen production catalyst in a three-electrode system for electrochemical testing, and the results are shown in Table 1.

[0076] Comparative Example 2

[0077] The nitrogen and phosphorus functionalized activated carbon support was prepared by the same method as in Example 1. 1 g of the nitrogen and phosphorus functionalized activated carbon support was dispersed in 350 ml of deionized water, and then 774 mg of cerium nitrate was added. The stirring was continued for 12 h. The solid product was separated by centrifugation or suction filtration, and then dried. The dried product was calcined at 800 °C under a hydrogen-argon mixed gas for 3 h in a tube furnace to obtain a composite support with different contents of cerium phosphate. The size of the cerium phosphate nanoparticles in the composite support was larger than that in the composite support of Example 1, and was between 7-20 nm.​​

[0078] 1 g of the above composite support was dispersed in 350 ml of deionized water, then 112 mg of potassium tetrachloroplatinate was added, and the mixture was stirred thoroughly for 8 h. After centrifugation or filtration, the mixture was dried. The resulting solid powder was reduced and calcined at 700 °C for 2 h under a hydrogen-argon mixture to obtain platinum-cerium alloy catalysts supported on the composite support with different cerium phosphate contents. The platinum content in the catalyst was 2.3% by mass, and the cerium content was 1.0% by mass.

[0079] The comparative catalyst was used as a catalyst for hydrogen production through water electrolysis in a three-electrode system for electrochemical testing. The electrochemical activity results are shown in Table 1.

[0080] Table 1. Hydrogen production activity tests of Examples 1-5, Comparative Examples 1-2, and commercial platinum-carbon catalysts in water electrolysis.

[0081] Serial number 10 mA / cm 2 time overpotential (mV) 100 mA / cm 2 time potential (mV) Example 1 13 41 Example 2 16 50 Example 3 20 60 Example 4 16 53 Example 5 15 58 Comparative Example 1 30 78 Comparative Example 2 24 74 Commercial platinum carbon 32 100

[0082] Table 1 shows the performance of Examples 1-5, Comparative Examples 1-2, and commercial platinum-carbon catalysts at 10 mA / cm². 2 and 100mA / cm 2 Overpotential comparison at current density. It can be seen that the electrocatalytic hydrogen evolution activity of the ultra-small platinum-rare earth alloy nanoclusters catalysts in Examples 1-4 is significantly higher than that of the unalloyed comparative example 1 catalyst, and also superior to the commercial platinum-carbon catalyst. Meanwhile, the content of rare earth components also affects the electrocatalytic hydrogen production performance. Example 5 shows that this preparation method is also applicable to other noble metals besides platinum.

[0083] Depend on Figure 5 As can be seen, compared with commercial platinum-carbon catalysts, the catalyst obtained in Example 1 exhibits superior hydrogen production performance in the PEM electrolyzer and has a lower water splitting voltage. More notably, the platinum content at the cathode of the electrolyzer assembled in Example 1 is only one-fifth that of the commercial catalyst, demonstrating a significant cost advantage.

[0084] Depend on Figure 6 It can be seen that, after prolonged water electrolysis, the size of the nanoclusters in the catalyst obtained in Example 1 is still less than 2 nm; from Figure 7 It can be seen that the commercial platinum-carbon catalyst exhibits obvious agglomeration and growth; this indicates that the catalyst in the example has excellent stability.

[0085] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a noble metal-rare earth alloy nanocluster catalyst, characterized by, The application relates to a preparation method of a noble metal-rare earth alloy nanocluster catalyst. 1) a carbon material, a nitrogen source and a phosphorus source are ball-mixed, roasted to obtain a nitrogen-phosphorus functionalized active carbon carrier; 2) the nitrogen-phosphorus functionalized active carbon carrier obtained in the step 1) is mixed with water and a rare earth salt, stirred, and the obtained solid is dried and then high-temperature roasted to obtain a composite carrier; 3) the composite carrier obtained in the step 2) is mixed with water and a noble metal salt, stirred, and the obtained solid is dried and then reduced and roasted to obtain a noble metal-rare earth alloy nanocluster catalyst; The carbon material in the step 1) is active carbon; The nitrogen source is urea, and the phosphorus source is a phytic acid solution with a mass percentage of 50%; The mass ratio of the carbon material to the nitrogen source and the phosphorus source is 5:1:6; The ball-mixing conditions in the step 1) include that the time is 1-3h, and the rotating speed is 100-600rpm; The roasting conditions include that the temperature is 800-1000 DEG C, and the time is 2h; The rare earth salt in the step 2) is cerium nitrate; The high-temperature roasting conditions in the step 2) are that the temperature is 600-900 DEG C, and the time is 1-3h; The noble metal salt in the step 3) is potassium tetrachloroplatinate; The loading percentage of the noble metal on the composite carrier is 2-10%; The reducing roasting conditions in the step 3) are that the temperature is 500-800 DEG C, and the time is 1-3h; The mass percentage of the noble metal in the noble metal-rare earth alloy nanocluster catalyst is 2.1%; The particle size of the noble metal-rare earth alloy nanocluster catalyst is 1.3-2.5nm; The noble metal-rare earth alloy nanocluster catalyst is used for proton exchange membrane electrolysis water hydrogen evolution.

2. The production method according to claim 1, characterized by, The loading percentage of the rare earth element on the nitrogen-phosphorus functionalized active carbon carrier in the step 2) is 5-20%.

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