Preparation method of anti-poisoning carbon-supported ternary alloy catalyst

Abstract

The invention relates to a preparation method of an anti-poisoning carbon-supported ternary alloy catalyst, and belongs to the technical field of fuel cell catalysts. According to the prepared carbon-supported ternary alloy catalyst, N and Pd are doped in the pretreated mesoporous carbon carrier through a hydrothermal method, S is introduced through treatment with p-toluenesulfonic acid, then Pt, Co and Pd are loaded on the surface of the carrier, and the prepared alloy catalyst has excellent catalytic performance and carbon monoxide poisoning resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of fuel cell catalysts and relates to a method for preparing a poison-resistant carbon-supported ternary alloy catalyst. Background Art

[0002] Fuel cells are one of the means of efficiently utilizing hydrogen energy. They have the advantages of high energy conversion rate, quiet operation, wide application range, safety and reliability. Since they were discovered, they have been widely concerned by people. When hydrogen-oxygen fuel cells are working, hydrogen is supplied to the hydrogen electrode, and oxygen is supplied to the oxygen electrode. Hydrogen and oxygen generate water through the electrolyte under the action of the catalyst on the electrode. Catalysts are an indispensable part of fuel cells. The commonly used catalyst at present is platinum-carbon catalyst, which has high catalytic activity and excellent corrosion resistance. Generally, the precious metal platinum is loaded on a carbon carrier. Platinum-carbon catalysts are expensive because of the high price of platinum. Moreover, platinum-carbon catalysts are very easy to adsorb carbon monoxide in hydrogen fuel and cause poisoning, which reduces the activity of the catalyst or even inactivates it.

[0003] Therefore, it is necessary to develop a multi-element alloy catalyst with high anti-poisoning ability that can be used in fuel cells. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing a carbon-supported ternary alloy catalyst resistant to poisoning. The prepared carbon-supported ternary alloy catalyst has excellent catalytic performance and resistance to carbon monoxide poisoning.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing a poison-resistant carbon-supported ternary alloy catalyst comprises the following preparation steps:

[0007] S1. Preparation of carrier:

[0008] S1.1, the mesoporous carbon was ultrasonically treated in 10wt.% potassium permanganate solution, deionized water and ethanol for 10min, and then the cleaned mesoporous carbon was dried in a drying oven at 60-70℃ for 18-24h;

[0009] S1.2. Palladium nitrate, NH4F, urea and p-toluenesulfonic acid in a molar ratio of 1:5:5:10 were fully mixed with deionized water to obtain a mixed solution A, stirred at 400 r / min at room temperature for 10 min, and then mesoporous carbon was added to fully immerse it in the mixed solution A, calcined at 120-150°C for 6-9 h, cooled naturally to room temperature, and the obtained solid was washed with deionized water and ethanol in turn, and dried in a vacuum drying oven at 60-70°C for 10-15 h to obtain solid A;

[0010] S1.3, solid A and dicyandiamide are mixed evenly in a mass ratio of 2:1, and then ground by a ball mill at a speed of 400r / min for 3h, and then heated to 400℃ at a rate of 5℃ / min in a nitrogen environment and maintained for h, and the heating rate is continued to increase to 800℃ and maintained for 2h to obtain the carrier;

[0011] S2, adding the carrier into the organic solvent and stirring at a speed of 350 r / min for 1 to 3 hours to obtain a carrier dispersion;

[0012] S3, adding a first metal salt, a second metal salt and a third metal salt into deionized water respectively to prepare a first solution, a second solution and a third solution, wherein the molar ratio of metal ions in the first solution, the second solution and the third solution is 1:1:1, the first metal is Pt, the second metal is Co, and the third metal is Pd;

[0013] S4, sequentially adding the first solution, the second solution and the third solution to the carrier dispersion, and mixing them uniformly by ultrasonic dispersion to obtain a mixed solution B;

[0014] S5, stirring the mixed solution B obtained in step S4 at a speed of 600 r / min, and heating at 85-95° C. until the deionized water is completely evaporated to obtain a solid intermediate;

[0015] S6. In an inert gas, heat the solid intermediate under vacuum conditions for 1 to 3 hours, and then heat and reduce it under a hydrogen atmosphere for 4 to 6 hours to obtain a poison-resistant carbon-supported ternary alloy catalyst.

[0016] As a preferred technical solution of the present invention, in step S2, the organic solvent is one of propanol, ethylene glycol, and isopropanol.

[0017] As a preferred technical solution of the present invention, in step S2, the usage ratio of the carrier to the organic solvent in the carrier dispersion is (3-5) mg: 2 mL.

[0018] As a preferred technical solution of the present invention, in step S3, the first metal salt is one of platinum chloride, platinum nitrate and platinum sulfate.

[0019] As a preferred technical solution of the present invention, in step S3, the second metal salt is one of cobalt nitrate, cobalt chloride and cobalt sulfate.

[0020] As a preferred technical solution of the present invention, in step S3, the third metal salt is one of palladium chloride, palladium nitrate and palladium sulfate.

[0021] As a preferred technical solution of the present invention, in step S4, the volume ratio of the first solution, the second solution and the third solution is 1:1:1.

[0022] As a preferred technical solution of the present invention, in step S4, the volume ratio of the carrier dispersion in the mixed solution B is (6-9):4.

[0023] As a preferred technical solution of the present invention, in step S6, the heating temperature under vacuum conditions is 130-150°C.

[0024] As a preferred technical solution of the present invention, in step S6, the temperature of the heating reduction is 400-500°C.

[0025] Before preparing the catalyst, the surface of the mesoporous carbon is modified by using potassium permanganate to add some oxygen-rich groups on the surface of the mesoporous carbon to increase the CO resistance of the alloy catalyst and its performance on the membrane electrode.

[0026] Mesoporous carbon was immersed in a mixed solution of zinc nitrate, NH4F, p-toluenesulfonic acid and urea, and solid A with a layered metal hydroxide structure grown on the surface of the mesoporous carbon was obtained by a hydrothermal method. Then, dicyandiamide was introduced as a nitrogen and carbon precursor, and the Pd metal alloy reduced by solid A during high-temperature calcination was used as a catalytic center to embed palladium metal nanoparticles into the nitrogen-doped mesoporous carbon carrier.

[0027] Introducing nitrogen into mesoporous carbon carrier materials can improve their electron transfer ability and chemical activity, thereby enhancing the catalyst's anti-poisoning ability. In addition, p-toluenesulfonic acid, as an organic sulfonic acid, will decompose during the roasting process to produce sulfur-containing gases. These gases will interact with the carbon carrier under high temperature conditions of roasting, including chemical adsorption, chemical reaction, etc., thereby introducing sulfur elements on the surface or inside the carbon carrier. This introduced sulfur element may be combined with the carbon carrier in the form of chemical bonds.

[0028] Therefore, nitrogen and sulfur can be introduced simultaneously on the mesoporous carbon support through the technical solution of the present invention. Nitrogen and sulfur doping can indirectly affect the adsorption and conversion process of CO by the catalyst by adjusting the electronic structure and surface properties of the catalyst. This adjustment helps to optimize the performance of the catalyst, making it show higher stability and activity when facing CO poisoning.

[0029] In addition, when preparing the ternary alloy catalyst, the carrier is first doped with palladium to form a palladium pre-deposition layer, so that the subsequent metal palladium can be more evenly dispersed on the carrier. The highly dispersed palladium can provide more catalytic active sites, thereby improving the catalytic efficiency.

[0030] Through the doping process, a stronger chemical bond or interaction can be formed between palladium and the carrier, thereby improving the stability of palladium on the carrier, resisting shedding or agglomeration during the reaction, and extending the service life of the catalyst. Due to the improved dispersion of palladium and the enhanced binding force between the carrier and palladium, the catalyst can provide more active sites and a more stable catalytic environment, which allows the reactants to more easily contact the active sites and be activated, thereby increasing the reaction rate.

[0031] The present invention prepares a ternary alloy catalyst, wherein Pt, Co and Pd are added to the catalyst, wherein Pt has high catalytic activity and can effectively reduce the activation energy of CO oxidation reaction, so that the reaction can be carried out at a lower temperature. The high activity helps to quickly oxidize CO on the catalyst surface, thereby reducing its poisoning effect; at the same time, since Pd is added to both the catalyst carrier and the activation component, the d energy band of Pt can be shifted downward, thereby weakening the interaction with the p orbital of CO, thereby reducing CO adsorption on the Pt surface, and further improving the catalyst's ability to resist CO poisoning.

[0032] At the same time, Co is added. The incorporation of Co can indirectly improve the catalyst's resistance to CO poisoning by adjusting the electronic structure of other metals in the catalyst and forming a special alloy structure through alloying. At the same time, doping with Co can not only modify the crystal surface structure of Pt, but also enhance the active sites of Pt and the activity of the catalyst, and can also improve the overall anti-poisoning property of the catalyst.

[0033] Beneficial effects of the present invention:

[0034] The carbon-supported ternary alloy catalyst prepared by the present invention is prepared by doping N and Pd in ​​a pretreated mesoporous carbon carrier by a hydrothermal method, introducing S by calcining with p-toluenesulfonic acid, and then loading Pt, Co and Pd on the surface of the carrier. The prepared alloy catalyst has excellent catalytic performance and resistance to carbon monoxide poisoning. DETAILED DESCRIPTION

[0035] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0036] The mesoporous carbon used in the present invention is CMK-3; palladium nitrate: purchased from Shandong Xiya Chemical Co., Ltd.; NH4F: purchased from Shanghai MacLean Biochemical Technology Co., Ltd., product number: A800956; p-toluenesulfonic acid: purchased from Shanghai Yien Chemical Technology Co., Ltd., product number: R032937; urea: purchased from Beijing Kangpu Huiwei Technology Co., Ltd.; dicyandiamide: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number: D100429; platinum chloride: purchased from Shanghai MacLean Biochemical Technology Co., Ltd., product number: P798899 ; Cobalt nitrate: purchased from Shanghai Eon Chemical Technology Co., Ltd.; Palladium chloride: purchased from Tianjin Xiensi Biochemical Technology Co., Ltd., product number: P-59032; Platinum nitrate: purchased from Shanghai MacLean Biochemical Technology Co., Ltd., product number: P799309; Cobalt chloride: purchased from Shanghai MacLean Biochemical Technology Co., Ltd., product number: C804815; Cobalt sulfate: purchased from Shanghai Eon Chemical Technology Co., Ltd., product number: R053043; Palladium sulfate: product number: purchased from Shanghai MacLean Biochemical Technology Co., Ltd., P815795.

[0037] Example 1

[0038] S1. Preparation of carrier:

[0039] S1.1, the mesoporous carbon was ultrasonically treated in 10wt.% potassium permanganate solution, deionized water and ethanol for 10min, and then the cleaned mesoporous carbon was dried in a drying oven at 60℃ for 18h;

[0040] S1.2. Palladium nitrate, NH4F, p-toluenesulfonic acid and urea in a molar ratio of 1:5:5:10 were fully mixed with deionized water to obtain a mixed solution A, and the mixture was stirred at a speed of 400 r / min at room temperature for 10 min. Then, mesoporous carbon was added to make it fully immersed in the mixed solution A, and the mixture was calcined at 120°C for 6 h. The mixture was naturally cooled to room temperature, and the obtained solid was washed with deionized water and ethanol in turn, and dried in a vacuum drying oven at 60°C for 10 h to obtain solid A.

[0041] S1.3, solid A and dicyandiamide in a mass ratio of 2:1 were ground by a ball mill at a speed of 400 r / min for 3 h, and then passed through a tubular furnace, heated to 400°C at a rate of 5°C / min in a nitrogen environment and maintained for h, and the heating rate was continued to increase to 800°C and maintained for 2 h to obtain the carrier;

[0042] S2, adding 300 mg of the carrier into 200 mL and stirring at a speed of 350 r / min for 1 h to obtain a carrier dispersion;

[0043] S3, respectively adding platinum chloride, cobalt nitrate and palladium chloride into deionized water to prepare a first solution, a second solution and a third solution, wherein the molar ratio of metal ions in the first solution, the second solution and the third solution is 1:1:1;

[0044] S4, sequentially adding the first solution, the second solution and the third solution in a volume ratio of 1:1:1 to the carrier dispersion liquid, and uniformly mixing them by ultrasonic dispersion to obtain a mixed solution B, wherein the volume ratio of the carrier dispersion liquid in the mixed solution B is 6:4;

[0045] S5, stirring the mixed solution obtained in step S4 at a speed of 600 r / min, and heating at 85-95° C. until the deionized water is completely evaporated to obtain a solid intermediate;

[0046] S6. In an inert gas, the solid intermediate is heated at 150° C. for 1 h under vacuum conditions, and then reduced at 400° C. for 6 h under a hydrogen atmosphere to obtain a poisoning-resistant carbon-supported ternary alloy catalyst.

[0047] Example 2

[0048] S1. Preparation of carrier:

[0049] S1.1, the mesoporous carbon was ultrasonically treated in 10wt.% potassium permanganate solution, deionized water and ethanol for 10min, and then the cleaned mesoporous carbon was dried in a drying oven at 65℃ for 21h;

[0050] S1.2. Palladium nitrate, NH4F, p-toluenesulfonic acid and urea in a molar ratio of 1:5:5:10 were fully mixed with deionized water to obtain a mixed solution A, and the mixture was stirred at a speed of 400 r / min at room temperature for 10 min. Then, mesoporous carbon was added to make it fully immersed in the mixed solution A, and the mixture was calcined at 130°C for 8 h. The mixture was naturally cooled to room temperature, and the obtained solid was washed with deionized water and ethanol in turn, and dried in a vacuum drying oven at 65°C for 13 h to obtain solid A.

[0051] S1.3, solid A and dicyandiamide in a mass ratio of 2:1 were ground by a ball mill at a speed of 400 r / min for 3 h, and then passed through a tubular furnace, heated to 400°C at a rate of 5°C / min in a nitrogen environment and maintained for h, and the heating rate was continued to increase to 800°C and maintained for 2 h to obtain the carrier;

[0052] S2, adding the carrier into propanol and stirring at a speed of 350 r / min for 2 h to obtain a carrier dispersion liquid, wherein the amount ratio of the carrier to the organic solvent in the carrier dispersion liquid is 4 mg: 2 mL;

[0053] S3, respectively adding platinum nitrate, cobalt chloride, and palladium nitrate into deionized water to prepare a first solution, a second solution, and a third solution, wherein the molar ratio of metal ions in the first solution, the second solution, and the third solution is 1:1:1;

[0054] S4, sequentially adding the first solution, the second solution and the third solution in a volume ratio of 1:1:1 to the carrier dispersion liquid, and uniformly mixing them by ultrasonic dispersion to obtain a mixed solution B, wherein the volume ratio of the carrier dispersion liquid in the mixed solution B is 7:4;

[0055] S5, stirring the mixed solution obtained in step S4 at a speed of 600 r / min, and heating at 90° C. until the deionized water is completely evaporated to obtain a solid intermediate;

[0056] S6. In an inert gas, the solid intermediate is heated at 140° C. for 2 h under vacuum conditions, and then reduced at 450° C. for 5 h under a hydrogen atmosphere to obtain a poisoning-resistant carbon-supported ternary alloy catalyst.

[0057] Example 3

[0058] S1. Preparation of carrier:

[0059] S1.1, the mesoporous carbon was ultrasonically treated in 10wt.% potassium permanganate solution, deionized water and ethanol for 10min, and then the cleaned mesoporous carbon was dried in a drying oven at 70℃ for 24h;

[0060] S1.2. Palladium nitrate, NH4F, p-toluenesulfonic acid and urea in a molar ratio of 1:5:5:10 were fully mixed with deionized water to obtain a mixed solution A, and the mixture was stirred at a speed of 400 r / min at room temperature for 10 min. Then, mesoporous carbon was added to make it fully immersed in the mixed solution A, and the mixture was calcined at 150°C for 9 h. The mixture was naturally cooled to room temperature, and the obtained solid was washed with deionized water and ethanol in turn, and dried in a vacuum drying oven at 70°C for 15 h to obtain solid A.

[0061] S1.3, solid A and dicyandiamide in a mass ratio of 2:1 were ground by a ball mill at a speed of 400 r / min for 3 h, and then passed through a tubular furnace, heated to 400°C at a rate of 5°C / min in a nitrogen environment and maintained for h, and the heating rate was continued to increase to 800°C and maintained for 2 h to obtain the carrier;

[0062] S2, adding the carrier into propanol and stirring at a speed of 350 r / min for 3 hours to obtain a carrier dispersion liquid, wherein the amount ratio of the carrier to the organic solvent in the carrier dispersion liquid is 5 mg: 2 mL;

[0063] S3, respectively adding platinum chloride, cobalt sulfate, and palladium sulfate into deionized water to prepare a first solution, a second solution, and a third solution, wherein the molar ratio of metal ions in the first solution, the second solution, and the third solution is 1:1:1;

[0064] S4, sequentially adding the first solution, the second solution and the third solution in a volume ratio of 1:1:1 to the carrier dispersion liquid, and uniformly mixing them by ultrasonic dispersion to obtain a mixed solution B, wherein the volume ratio of the carrier dispersion liquid in the mixed solution B is 6:4;

[0065] S5, stirring the mixed solution obtained in step S4 at a speed of 600 r / min, and heating at 95° C. until the deionized water is completely evaporated to obtain a solid intermediate;

[0066] S6. In an inert gas, the solid intermediate is heated at 150°C for 1 h under vacuum conditions, and then reduced at 500°C for 4 h under a hydrogen atmosphere to obtain a poisoning-resistant carbon-supported ternary alloy catalyst.

[0067] Comparative Example 1

[0068] The difference between Comparative Example 1 and Example 1 is that p-toluenesulfonic acid is not added in step S1.2 of Comparative Example 1, and the other operations are the same.

[0069] Comparative Example 2

[0070] The difference between Comparative Example 2 and Example 1 is that step S1.2 is not performed in Comparative Example 2, and the remaining operations are the same.

[0071] Comparative Example 3

[0072] The difference between Comparative Example 3 and Example 1 is that steps S1.2 and S1.3 are not performed in Comparative Example 3, and the remaining operations are the same.

[0073] Performance Testing:

[0074] 1. The cyclic voltammetry (CV) curve and the linear sweep voltammetry (LSV) curve of the catalyst obtained in each embodiment and comparative example were tested by rotating disk electrode (RDE). The experimental conditions of the rotating disk electrode test were as follows: at room temperature, 5 mg ± 0.05 mg of the catalyst was weighed, 2 mL of deionized water, 2 mL of isopropanol, and 50 μL of 5% Nafion (DE521) were added in sequence to form a uniform and stable suspension, 10 μL of the suspension was dropped onto the surface of a glassy carbon electrode with a diameter of 4 mm to prepare a working electrode; a reversible hydrogen electrode (RDE) was used as a reference electrode; a platinum electrode was used as a counter electrode; the electrolyte was a 0.1 mol / L HClO4 solution;

[0075] The obtained catalyst was subjected to a cyclic voltammetry curve test to obtain the electrochemical active area of ​​the catalyst. The experimental conditions for the cyclic voltammetry curve test were: a scanning interval of 0.01 to 1.15 V, a scanning speed of 20 mV / s; the experimental conditions for the linear scanning voltammetry curve test were: a scanning interval of 0.2 to 1.0 V, a scanning speed of 5 mV / s, and an RDE rotation speed of 1600 rpm. A linear scanning voltammetry curve was obtained. The test results are shown in Table 1 below:

[0076] Table 1

[0077]

[0078] 2. Test Examples and Comparative Examples Hydrogen Oxidation Reaction HOR performance under different concentrations of carbon monoxide, the electrolyte is 0.1 mol / L KOH solution, the potential is 50 (mV vs. RHE), the test results are shown in Table 2:

[0079] Table 2

[0080]

[0081] According to the above data, the electrochemically active area of ​​Examples 1-3 is larger than that of Comparative Examples 1-3, so the Examples have better electrochemical performance. At the same carbon monoxide concentration, the area specific activity and mass specific activity of the catalyst of the Comparative Example are much smaller than the area specific activity of the catalyst prepared in the Examples. Under the same test conditions, the HOR performance of the ternary alloy catalyst is better than the HOR performance of the comparative example catalyst. Therefore, the catalyst prepared by the present invention has excellent resistance to CO poisoning.

[0082] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a poison-resistant carbon-supported ternary alloy catalyst, characterized in that: The method comprises the following preparation steps: S1. Preparation of carrier: S1.1, the mesoporous carbon was ultrasonically treated in 10wt.% potassium permanganate solution, deionized water and ethanol for 10min, and then the cleaned mesoporous carbon was dried in a drying oven at 60-70℃ for 18-24h; S1.

2. Palladium nitrate, NH4F, urea and p-toluenesulfonic acid in a molar ratio of 1:5:5:10 were fully mixed with deionized water to obtain a mixed solution A, stirred at 400 r / min at room temperature for 10 min, and then mesoporous carbon was added to fully immerse it in the mixed solution A, calcined at 120-150°C for 6-9 h, cooled naturally to room temperature, and the obtained solid was washed with deionized water and ethanol in turn, and dried in a vacuum drying oven at 60-70°C for 10-15 h to obtain solid A; S1.3, solid A and dicyandiamide are mixed evenly in a mass ratio of 2:1, and then ground by a ball mill at a speed of 400r / min for 3h, and then heated to 400℃ at a rate of 5℃ / min in a nitrogen environment and maintained for h, and the heating rate is continued to increase to 800℃ and maintained for 2h to obtain the carrier; S2, adding the carrier into the organic solvent and stirring at a speed of 350 r / min for 1 to 3 hours to obtain a carrier dispersion; S3, adding a first metal salt, a second metal salt and a third metal salt into deionized water respectively to prepare a first solution, a second solution and a third solution, wherein the molar ratio of metal ions in the first solution, the second solution and the third solution is 1:1:1, the first metal is Pt, the second metal is Co, and the third metal is Pd; S4, sequentially adding the first solution, the second solution and the third solution to the carrier dispersion, and mixing them uniformly by ultrasonic dispersion to obtain a mixed solution B; S5, stirring the mixed solution B obtained in step S4 at a speed of 600 r / min, and heating at 85-95° C. until the deionized water is completely evaporated to obtain a solid intermediate; S6. In an inert gas, heat the solid intermediate under vacuum conditions for 1 to 3 hours, and then heat and reduce it under a hydrogen atmosphere for 4 to 6 hours to obtain a poisoning-resistant carbon-supported ternary alloy catalyst.

2. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S2, the organic solvent is one of propanol, ethylene glycol and isopropanol.

3. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S2, the ratio of the amount of the carrier to the amount of the organic solvent in the carrier dispersion is (3-5) mg: 2 mL.

4. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S3, the first metal salt is one of platinum chloride, platinum nitrate and platinum sulfate.

5. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S3, the second metal salt is one of cobalt nitrate, cobalt chloride and cobalt sulfate.

6. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S3, the third metal salt is one of palladium chloride, palladium nitrate and palladium sulfate.

7. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S4, the volume ratio of the first solution, the second solution and the third solution is 1:1:

1.

8. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S4, the volume ratio of the carrier dispersion in the mixed solution B is (6-9):

4.

9. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S6, the heating temperature under the vacuum condition is 130-150°C.

10. The method for preparing the poison-resistant carbon-supported ternary alloy catalyst according to claim 1, characterized in that: In step S6, the temperature of the heating reduction is 400-500°C.

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