Hydrogen fuel cell catalyst for resisting carbon monoxide poisoning and preparation method thereof

Abstract

The invention relates to a carbon monoxide poisoning resistant hydrogen fuel cell catalyst and a preparation method thereof, and belongs to the technical field of fuel cell catalysts. The catalyst is composed of a modified carbon carrier, an active component and an auxiliary component, the active component is Pt, and the auxiliary components are Ti and Ru; the catalyst not only has good dispersibility of active components and good mass activity, but also has good CO poisoning resistance. According to the method, the modification of the ruthenium and titanium composite oxide on the carbon carrier is completed in one step by adopting a ball milling method, and the structural stability of the carbon carrier and the CO poisoning resistance of the catalyst are enhanced while abundant Pt anchoring sites are provided; according to the ball-milling process, high dispersion of ruthenium, titanium oxide and Pt on a carbon carrier is promoted by adding a small amount of grinding aid instead of using a solvent, so that generation of waste liquid is effectively reduced, and the greenization degree of the production process is improved.

Description

Technical Field

[0001] This invention relates to a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning and its preparation method, belonging to the field of fuel cell catalyst technology. Background Technology

[0002] Hydrogen fuel cells are key equipment for hydrogen energy applications. As an energy conversion device, they directly convert the chemical energy of fuel into electrical energy. Catalysts are the core materials of hydrogen fuel cells, with platinum-carbon (Pt / C) catalysts being the most commonly used. Studies have shown that even ppm-level carbon monoxide (CO) can cause a sharp decline in catalyst activity. Currently, large-scale hydrogen (H2) production is mainly achieved through reforming reactions of petroleum and natural gas, as well as incomplete combustion and shift reactions of coal, all of which contain a certain amount of CO. Furthermore, the carbon support used in Pt / C catalysts is generally a porous carbon support with a high specific surface area. Its surface has a large number of unsaturated bonds and defects, making it prone to electrochemical oxidation corrosion that generates CO, thus causing Pt poisoning. Therefore, solving the CO poisoning problem of Pt-based catalysts is crucial for the development of hydrogen fuel cells.

[0003] Numerous studies have demonstrated that forming nanoalloys with Pt and other metals can enhance its resistance to CO poisoning. Currently, the most promising catalysts with high activity and strong CO poisoning resistance are binary alloy catalysts composed of any one of Mo, W, Os, or Ru with Pt, with Pt-Ru binary alloy catalysts being the best. It is generally believed that Ru readily forms active oxygen-containing species with water, which promotes the oxidation reaction on the Pt surface, thereby improving the catalyst's activity and poisoning resistance. Another view suggests that the addition of Ru modulates the d-electron state of Pt, weakening the interaction between Pt and CO and thus enhancing the catalyst's poisoning resistance.

[0004] Existing PtRu / C catalysts typically have a total metal loading of ≥20 wt.%, and achieving good dispersion and performance of the loaded components requires sophisticated preparation processes. The impregnation-reduction method is simpler to operate and easier to scale up than colloidal, microemulsion, and ion exchange methods. However, the impregnation washing and purification step is prone to metal loss. Chinese patent CN120164970A uses a variety of organic reagents as solvents to prepare a PtRu catalyst with strong resistance to CO poisoning, but the generated organic waste liquid has a great impact on the environment. In addition, the water and ion radii of Pt and Ru precursors are large, making it difficult to enter the pores of the support. Therefore, the dispersion of Pt and Ru in the obtained catalyst is difficult to control, and the uneven distribution of components makes it difficult to obtain a high-quality alloyed catalyst. Chinese patent CN101912778A uses microwave-assisted drying to improve the dispersion effect of Pt and the second component metals such as Pd and Ru. However, the low-temperature dry impregnation adsorption step involved in its process needs to be carried out at -5 ℃ for 24 h to 36 h, which takes a long time and is difficult to achieve with conventional scale-up equipment. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, the present invention aims to provide a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning and its preparation method. The catalyst not only exhibits good dispersibility of its active components and excellent mass activity, but also demonstrates strong resistance to CO poisoning; the method produces minimal waste liquid and is environmentally friendly.

[0006] To achieve the objectives of this invention, the following technical solutions are provided.

[0007] A hydrogen fuel cell catalyst resistant to carbon monoxide poisoning, the catalyst comprising a modified carbon support, an active component, and auxiliary components; the active component is platinum (Pt), and the auxiliary components are titanium (Ti) and ruthenium (Ru). Furthermore, based on the total mass of the catalyst (100%), the mass fraction of Pt as metal is 20% to 55%, the mass fraction of Ti as oxide is 0.5% to 15%, and the Pt / Ru ratio is 3 to 0.5.

[0008] A method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning according to the present invention, the method comprising the following steps: (1) Carbon support pretreatment The carbon support powder was prepared into a solution, heated under reflux, and then filtered to remove impurities. The solution was then dried at 70℃ to 95℃ for 2 to 6 hours. The dried carbon support and a 10% to 45% nitric acid solution (liquid-to-solid ratio of 5 g / ml to 25 g / ml) were then added to a ball mill jar, and the mixture was ball-milled for 1 to 6 hours to obtain the pretreated carbon support. The carbon support is a conventional carbon support in the art, such as XC-72 carbon black, MWCNTS, mesoporous carbon material CMK-1, and acetylene black.

[0009] (2) Modified carbon support Isopropanol and titanium (Ti) source were thoroughly stirred to prepare solution A, and ethanol and ruthenium (Ru) source were thoroughly stirred to prepare solution B. Then, solutions A and B were added to a ball mill jar, and citric acid and hydrogen peroxide were added as grinding aids. After ball milling, the pretreated activated carbon obtained in step (1) was added, and ball milling was continued for 1 h ~ 6 h. After drying, the carbon was calcined at 180 ° C ~ 450 ° C for 2 h ~ 8 h under a nitrogen atmosphere to prepare the modified carbon support. Furthermore, when the mass fraction of hydrogen peroxide is 25%, the mass ratio of hydrogen peroxide, citric acid, and modified carbon support is 0.05 : 0.1 : 1 ~ 0.5 : 0.1 : 1; Drying is carried out at 110℃ for 1 h to 6 h.

[0010] (3) Preparation of Pt-based catalysts The Pt precursor and the modified carbon support obtained in step (2) were added to a ball mill jar for ball milling. Citric acid and hydrogen peroxide were then added as grinding aids. The mixture was ball milled for 1 h to 6 h, dried, and then heated to 120 ℃ to 350 ℃ at a heating rate of 2 ℃ / min to 10 ℃ / min. Hydrogen gas was introduced for reduction for 0.5 h to 6 h to obtain a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning. Furthermore, when the mass fraction of hydrogen peroxide is 25%, the mass ratio of hydrogen peroxide, citric acid, and modified carbon support is 0.05 : 0.1 : 1 ~ 0.5 : 0.1 : 1; Drying is carried out at 110℃ for 1 h to 6 h; The hydrogen flow rate is 10 ml / min ~ 30 ml / min.

[0011] Furthermore, the mass of Pt in the Pt precursor is 20% to 55% of the catalyst mass; Furthermore, the Pt precursor is H2PtCl6, Pt(NO3)2, H2Pt(OH)6 or Na6Pt(SO3)4; preferably, the Pt precursor is platinum nitrate or H2Pt(OH)6; Furthermore, the Ti source is titanium tetrachloride, tetrabutyl titanate, tetraethyl titanate, or titanium isopropoxide; Furthermore, the Ru source is RuCl3, Ru(NO)(NO3)3, or Ru(OAC). x ; Furthermore, the preferred mass ratio of hydrogen peroxide, citric acid, and modified carbon support is 0.1:0.1:1 to 0.3:0.1:1; Furthermore, the preferred ball milling time is 1.5 h to 4 h; Furthermore, it is preferable to reduce the hydrogen gas at 150 ℃ ~ 300 ℃ for 2 h ~ 4 h.

[0012] An application of the hydrogen fuel cell catalyst resistant to carbon monoxide poisoning according to the present invention is described, wherein the application involves using the catalyst in a CO poisoning resistance test for H2 electrocatalytic oxidation; the specific application method is as follows: The working electrode substrate was a 5 mm diameter glassy carbon electrode (GC). The GC electrode was polished to a mirror finish on metallographic sandpaper and Al2O3 powder. 10 mg of the catalyst was weighed and ultrasonically dispersed in 2 ml of anhydrous ethanol. 10 μL of the suspension was dropped onto the surface of the GC electrode and dried at 60 °C. Then, 8 μL of 5% Nation solution was transferred to the electrode surface and dried at 60 °C. The actual catalyst loading on the electrode was calculated based on the concentration and volume of the ink used. An electrolytic cell was constructed using 0.1 M HClO4 solution as the electrolyte, a platinum sheet as the counter electrode, and a saturated calomel electrode (SCE) as the reference electrode. Before the CV test, N2 was bubbled into the electrolyte solution for 15 min to remove dissolved O2. The current density was scanned at 50 mV / s from -0.2 V to 1.2 V until it no longer increased. Then, the catalyst was subjected to CV tests at 100 mV / s from 0.6 V to 1.0 V under H2 atmosphere and a CO / H2 mixture, respectively. The catalyst activity I was determined based on the mass ratio of the catalyst after the H2 reaction and the CO / H2 reaction. a I b and its changes, the changes being in I b / I a This represents the change in electrochemical area, specifically the electrochemical area S after the H2 reaction. a Electrochemical area S after reaction with a mixture of CO and H2 gas b , with S b / S a Indicates; to evaluate catalyst performance and resistance to CO poisoning, I b / I a and S b / S a The closer the ratio is to 1, the stronger the catalyst's resistance to CO poisoning.

[0013] Beneficial effects (1) The present invention provides a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning. The catalyst is composed of a modified carbon support, an active component Pt and an auxiliary component. It not only has good mass activity, but also has a good resistance to CO poisoning. (2) This invention provides a method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning. Carbon supports are usually generated by oxidation activation process to increase the number of Pt anchoring sites by generating defect sites such as carbonyl and carboxyl groups. However, this will reduce the stability of the carbon support and thus have an adverse effect on the stability of the catalyst. The method described in this invention uses ball milling to modify the carbon support with ruthenium and titanium composite oxides in one step. While providing abundant Pt anchoring sites, it enhances the structural stability of the carbon support and the catalyst's ability to resist CO poisoning. This ball milling process promotes the high dispersion of ruthenium, titanium oxides and Pt on the carbon support by adding a small amount of grinding aid instead of using solvents, effectively reducing the generation of waste liquid and improving the greenness of the production process. (3) The present invention provides a method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning. The preparation method uses a ball milling process to adjust the uniformity of the carbon support particles. Under the condition of using less or no water, the modification of the carbon support and the highly dispersed loading of auxiliary components can be completed in one step, reducing the defect sites of the activated carbon support to inhibit the electrochemical oxidation corrosion reaction. Combined with TiO2 with a high dielectric constant, the conductivity of the catalyst is guaranteed. On the other hand, oxygen-rich TiO2 and RuO2 are formed, thereby adjusting the electronic structure of the loaded Pt, reducing the adsorption of CO on Pt, and improving the catalyst's ability to resist CO poisoning. (4) The present invention provides a method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning. The preparation method is simple and generates less wastewater. It can conveniently and cleanly combine modified carbon support, active components and auxiliary components to prepare a catalyst to meet the actual use requirements. Detailed Implementation

[0014] The present invention will be described in detail below with reference to specific embodiments, but this is not intended to limit the scope of the present invention.

[0015] In the following examples, the method for evaluating the activity of H2 electrocatalytic oxidation in resisting CO poisoning is as follows: The working electrode substrate was a 5 mm diameter glassy carbon electrode (GC). The GC electrode was polished to a mirror finish on metallographic sandpaper and Al2O3 powder. 10 mg of the catalyst was weighed and ultrasonically dispersed in 2 ml of anhydrous ethanol. 10 μL of the suspension was dropped onto the surface of the GC electrode and dried at 60 °C. Then, 8 μL of 5% Nation solution was transferred to the electrode surface and dried at 60 °C. The actual catalyst loading on the electrode was calculated based on the concentration and volume of the ink used. An electrolytic cell was constructed using 0.1 M HClO4 solution as the electrolyte, a platinum sheet as the counter electrode, and a saturated calomel electrode (SCE) as the reference electrode. Before the CV test, N2 was bubbled into the electrolyte solution for 15 min to remove dissolved O2. The current density was scanned at 50 mV / s from -0.2 V to 1.2 V until it no longer increased. Then, the catalyst was subjected to CV tests at 100 mV / s from 0.6 V to 1.0 V under H2 atmosphere and a CO / H2 mixture, respectively. The catalyst activity I was determined based on the mass ratio of the catalyst after the H2 reaction and the CO / H2 reaction. a I b and its changes, the changes being in I b / I a This represents the change in electrochemical area, specifically the electrochemical area S after the H2 reaction. a Electrochemical area S after reaction with a mixture of CO and H2 gas b , with S b / S a Indicates; to evaluate catalyst performance and resistance to CO poisoning, I b / I a and S b / S a The closer the ratio is to 1, the stronger the catalyst's resistance to CO poisoning.

[0016] Example 1 (1) Carbon nanotubes were added to acetone to prepare a solution, refluxed at 85 °C for 4 h, and then filtered and washed with ethanol at twice the volume of acetone to remove impurities on the surface of the carbon nanotubes. The solution was dried at 95 °C for 4 h. Then, the dried carbon nanotubes and a 30% nitric acid solution were added to a ball mill jar and ball milled for 2 h to obtain pretreated carbon nanotubes.

[0017] (2) Measure 10 ml of isopropanol into a 100 ml beaker, add 3.2 g of tetrabutyl titanate into the beaker, stir for 30 min, and prepare solution A; measure 15 ml of ethanol into a 100 ml beaker, add 8.7 g of ruthenium nitrate into the beaker, stir for 30 min, and prepare solution B; Solution A and solution B were added to a ball mill jar, along with 0.93 g of 25% hydrogen peroxide and 0.31 g of citric acid as grinding aids. The mixture was ball-milled for 10 min, then 3.15 g of pretreated carbon nanotubes were added, and the mixture was ball-milled for another 1.5 h. The mixture was then dried at 110 ℃ for 4 h and calcined at 280 ℃ for 3 h under a nitrogen atmosphere to obtain modified carbon nanotubes. (3) Add 5 g of platinum nitrate and 7.5 g of modified carbon nanotubes to a ball mill jar and ball mill for 5 min. Then add 0.93 g of hydrogen peroxide with a mass fraction of 25% and 0.31 g of citric acid, ball mill for 1.5 h, then dry at 110 ℃ for 4 h, then heat to 150 ℃ at a heating rate of 5 ℃ / min, and treat with hydrogen gas for 2 h to obtain a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning, denoted as Cat-1.

[0018] Performance testing: The activity of Cat-1 in the anti-CO poisoning reaction of H2 electrocatalytic oxidation was evaluated. After 3000 cycles of H2 purging, its mass-to-activity ratio I was [missing information]. a It is 0.91 A / mg Pt Electrochemical area S a 83 m 2 / g, after reacting with a mixture of CO and H2 gas for 3000 cycles, its mass ratio to activity I b It is 0.85 mA / g Pt Electrochemical area S a It is 77.2 m 2 / g, I b / I a = 0.93, S b / S a = 0.93.

[0019] Example 2 Based on Example 1, titanium butyl ester was replaced with titanium isopropoxide, and other operations were the same as in Example 1, resulting in a catalyst denoted as Cat-2.

[0020] Performance testing: The activity of Cat-2 in the anti-CO poisoning reaction by H2 electrocatalytic oxidation was evaluated. After 3000 cycles of H2 purging, its mass-to-activity ratio I was [missing information]. a 0.90A / mg Pt Electrochemical area S a 83 m 2 / g, after reacting with a mixture of CO and H2 gas for 3000 cycles, its mass ratio to activity I b It is 0.84 A / mg Pt Electrochemical area S bIt is 76.1 m 2 / g, I b / I a = 0.93, S b / S a = 0.92.

[0021] Example 3 Based on Example 1, ruthenium nitrate was replaced with ruthenium acetate, the amount of hydrogen peroxide in steps (1) and (2) was adjusted to 0.31 g, and other operations were the same as in Example 1. The resulting catalyst was denoted as Cat-3.

[0022] Performance testing: The activity of Cat-3 in the anti-CO poisoning reaction of H2 electrocatalytic oxidation was evaluated. After 3000 cycles of H2 purging, its mass-to-activity ratio I was [missing information]. a It is 0.9 A / mg Pt Electrochemical area S a 81 m 2 / g, after reacting with a mixture of CO and H2 gas for 3000 cycles, its mass ratio to activity I b It is 0.82 A / mg Pt Electrochemical area S b It is 72.1 m 2 / g, I b / I a = 0.91, S b / S a = 0.89.

[0023] Example 4 Based on Example 1, the amount of ruthenium nitrate in step (2) was adjusted from 8.7 g to 4.7 g, the amount of pretreated carbon nanotubes was adjusted to 4.4 g, and other operations were the same as in Example 1. The resulting catalyst was denoted as Cat-4.

[0024] Performance testing: The activity of Cat-4 in the anti-CO poisoning reaction of H2 electrocatalytic oxidation was evaluated. After 3000 cycles of H2 purging, its mass-to-activity ratio I was [missing information]. a It is 0.88 A / mg Pt Electrochemical area S a 81 m 2 / g, after reacting with a mixture of CO and H2 gas for 3000 cycles, its mass ratio to activity I b It is 0.77 A / mg Pt Electrochemical area S b 70.5 m 2 / g, I b / I a= 0.88, S b / S a = 0.87.

[0025] Example 5 Based on Example 1, the amount of 3.2 g of tetrabutyl titanate in step (2) was adjusted to 1.6 g, the amount of pretreated carbon nanotubes was adjusted to 3.52 g, and other operations were the same as in Example 1. The resulting catalyst was denoted as Cat-5.

[0026] Performance testing: The activity of Cat-5 in the anti-CO poisoning reaction by H2 electrocatalytic oxidation was evaluated. After 3000 cycles of H2 purging, its specific activity Ia was 0.83 A / mg. Pt Electrochemical area S a 78 m 2 / g, after reacting with a mixture of CO and H2 gas for 3000 cycles, its mass ratio to activity I b It is 0.71 A / mg Pt Electrochemical area S b It is 64.7 m 2 / g, I b / I a = 0.86, S b / S a = 0.83.

[0027] Example 6 Based on Example 1, the ball milling time was adjusted to 3 h, the reduction temperature in step (3) was adjusted from 150 ℃ to 300 ℃, and other operations were the same as in Example 1. The resulting catalyst was denoted as Cat-6.

[0028] Performance testing: The activity of Cat-6 in the anti-CO poisoning reaction of H2 electrocatalytic oxidation was evaluated. After 3000 cycles of H2 purging, its mass-to-activity ratio I was [missing information]. a It is 0.83 A / mg Pt Electrochemical area S a 80 m 2 / g, after reacting with a mixture of CO and H2 gas for 3000 cycles, its mass ratio to activity I b It is 0.75 A / mg Pt Electrochemical area S b It is 72.1 m 2 / g, I b / I a = 0.9, S b / S a = 0.9.

[0029] Comparative Example 1 Based on Example 1, the tetrabutyl titanate in step (2) is removed, and the other operations are the same as in Example 1.

[0030] Comparative Example 2 Based on Example 1, ruthenium nitrate in step (2) is removed, and other operations are the same as in Example 1.

[0031] Comparative Example 3 Based on Example 1, the amount of ruthenium nitrate in step (2) was adjusted from 8.7 g to 0.35 g, and the other operations were the same as in Example 1.

[0032] Comparative Example 4 Based on Example 1, the amount of 3.2 g of tetrabutyl titanate in step (2) was adjusted to 0.26 g, and other operations were the same as in Example 1.

[0033] Comparative Example 5 Based on Example 1, the reduction temperature in step (3) was adjusted from 150 ℃ to 350 ℃, and other operations were the same as in Example 1.

[0034] Comparative Example 6 Based on Example 1, the grinding aid was removed, and other operations were the same as in Example 1.

[0035] Performance Test Summary The catalysts obtained in Examples 1-6 and Comparative Examples 1-6 were used to evaluate the activity of the H2 electrocatalytic oxidation reaction against CO poisoning. Catalyst performance tests were conducted under pure H2 atmosphere and 500 ppm CO / H2 mixed gas conditions. After purging with N2 gas, CV scans were performed 1000 times under each atmosphere. The change in the mass-specific activity of the catalyst after 1000 CV scans (Ig) was used as the metric. b / I a ) and changes in electrochemical active area (S b / S a ) indicates CO resistance, I b / I a and S b / S a The closer the ratio is to 1, the stronger the catalyst's resistance to CO poisoning. The test results are shown in Table 1.

[0036] Table 1

[0037] The test results in Table 1 show that, in the above embodiments of the present invention, with variations in the types and contents of the carbon support modifier ruthenium oxide and titanium oxide precursors as one condition, the grinding aid used as another condition, and the reduction temperature of the Pt catalyst preparation as a third condition, within the range described in the claims, its electrocatalytic oxidation ability for H2 is significant, and it also exhibits good resistance to CO poisoning. In the above comparative embodiments of the present invention, when the variation conditions are adjusted to outside the scope of the claims, its resistance to CO poisoning is significantly reduced.

[0038] This invention includes, but is not limited to, the above embodiments. Any equivalent substitutions or partial improvements made under the spirit and principles of this invention shall be considered to be within the scope of protection of this invention.

Claims

1. A hydrogen fuel cell catalyst resistant to carbon monoxide poisoning, characterized in that: The catalyst is composed of a modified carbon support, an active component, and auxiliary components; the active component is Pt, and the auxiliary components are Ti and Ru.

2. The hydrogen fuel cell catalyst resistant to carbon monoxide poisoning according to claim 1, characterized in that: Based on the total mass of the catalyst (100%), Pt (as metal) has a mass fraction of 20% to 55%, Ti (as oxide) has a mass fraction of 0.5% to 15%, and the Pt / Ru ratio is 3 to 0.

5.

3. A method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning as described in claim 1 or 2, characterized in that: (1) Prepare a solution of carbon carrier powder, heat and reflux it, then filter and wash to remove impurities from the carbon carrier, and dry it at 70℃~95℃ for 2h~6h; then add the dried carbon carrier and a 10%~45% nitric acid solution to the ball mill jar, with a liquid-solid ratio of 5 g / ml~25 g / ml, and ball mill for 1h~6h to obtain the pretreated carbon carrier; (2) Mix isopropanol and Ti source thoroughly to prepare solution A, and mix ethanol and Ru source thoroughly to prepare solution B; Then, solutions A and B were added to a ball mill jar, and citric acid and hydrogen peroxide were added as grinding aids. After ball milling, pretreated activated carbon was added, and ball milling continued for 1 h to 6 h. After drying, the modified carbon carrier was calcined at 180 ℃ to 450 ℃ for 2 h to 8 h under a nitrogen atmosphere. (3) Add the Pt precursor and modified carbon support to a ball milling jar and ball mill. Then add citric acid and hydrogen peroxide as grinding aids and ball mill for 1 h ~ 6 h. Dry the mixture and then heat it to 120 ℃ ~ 350 ℃ at a heating rate of 2 ℃ / min ~ 10 ℃ / min. Then introduce hydrogen gas to reduce it for 0.5 h ~ 6 h to obtain a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning.

4. The method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning according to claim 3, characterized in that: The carbon carrier is XC-72 carbon black, MWCNTS, mesoporous carbon material CMK-1, or acetylene black; The Pt precursors are H2PtCl6, Pt(NO3)2, H2Pt(OH)6 or Na6Pt(SO3)4; The Ti source is titanium tetrachloride, tetrabutyl titanate, tetraethyl titanate, or titanium isopropoxide. The Ru source is RuCl3, Ru(NO)(NO3)3, or Ru(OAC). x .

5. The method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning according to claim 3, characterized in that: In steps (2) and (3), when the mass fraction of hydrogen peroxide is 25%, the mass ratio of hydrogen peroxide, citric acid and modified carbon carrier is 0.05:0.1:1 ~ 0.5:0.1:1; and drying is carried out at 110℃ for 1 h ~ 6 h.

6. A method for preparing a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning according to any one of claims 3 to 5, characterized in that: The hydrogen flow rate is 10 ml / min ~ 30 ml / min; The mass of Pt in the Pt precursor is 20% to 55% of the catalyst mass; The mass ratio of hydrogen peroxide, citric acid, and modified carbon support is 0.1:0.1:1 to 0.3:0.1:

1. The ball milling time is 1.5 h to 4 h; Reduce with hydrogen gas at 150 ℃ ~ 300 ℃ for 2 h ~ 4 h.

7. The application of a hydrogen fuel cell catalyst resistant to carbon monoxide poisoning as described in claim 1 or 2, characterized in that: The application is to use the catalyst in a CO poisoning test for the electrocatalytic oxidation of H2.

8. The application of the hydrogen fuel cell catalyst resistant to carbon monoxide poisoning according to claim 7, characterized in that: The application method is as follows: The working electrode substrate is a glassy carbon electrode with a diameter of 5 mm. The glassy carbon electrode is polished to a mirror finish on metallographic sandpaper and Al2O3 powder. 10 mg of the catalyst is weighed, and 2 ml of anhydrous ethanol is added for ultrasonic dispersion. 10 μL of the suspension is dropped onto the surface of the glassy carbon electrode and dried at 60 °C. Then, 8 μL of 5% Nation solution is transferred to the electrode surface and dried at 60 °C. The actual catalyst loading on the electrode is calculated based on the concentration and volume of the ink used. An electrolytic cell is formed using 0.1 M HClO4 solution as the electrolyte, a platinum sheet as the counter electrode, and a saturated calomel electrode (SCE) as the reference electrode. Before the CV test, N2 was bubbled into the electrolyte solution for 15 min to remove dissolved O2. The current density was scanned at 50 mV / s from -0.2 V to 1.2 V until it no longer increased. Then, the catalyst was subjected to CV tests at 100 mV / s from 0.6 V to 1.0 V under H2 atmosphere and a CO / H2 mixture, respectively. The catalyst activity I was determined based on the mass ratio of the catalyst after the H2 reaction and the CO / H2 reaction. a I b and its changes, the changes being in the form of I b / I a This represents the change in electrochemical area, specifically the electrochemical area S after the H2 reaction. a Electrochemical area S after reaction with a mixture of CO and H2 gas b , with S b / S a Indicates; to evaluate catalyst performance and resistance to CO poisoning, I b / I a and S b / S a The closer the ratio is to 1, the stronger the catalyst's resistance to CO poisoning.

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