A proton exchange membrane hydrogen pump anode and its use

Abstract

This invention discloses a proton exchange membrane hydrogen pump anode and its application. The anode includes an anode sheet and a catalyst composited on the anode sheet. The catalyst includes a support and a first metal and a second metal composited on the support. The first metal is selected from one or more of platinum, iridium, palladium, and ruthenium; the second metal is selected from one or more of iron, cobalt, nickel, molybdenum, and vanadium. The first metal serves as the main active center for the hydrogen oxidation reaction, and the second metal can regulate the electronic structure of the first metal, thereby reducing the adsorption of carbon monoxide at the active site or promoting its oxidative removal. The synergistic effect of the two metals allows the anode containing the catalyst to maintain high hydrogen oxidation activity and stability in hydrogen fuel containing carbon monoxide, thereby improving the carbon monoxide poisoning resistance of the proton exchange membrane hydrogen pump containing the anode.

Description

Technical Field

[0001] This invention relates to the field of electrochemical hydrogen purification technology, and in particular to a proton exchange membrane hydrogen pump anode and its application. Background Technology

[0002] Hydrogen energy, as a clean and efficient renewable energy source, is considered an important energy carrier for adjusting the global energy structure and improving energy efficiency. However, in my country's hydrogen production structure, coal-based hydrogen accounts for more than half. Due to the influence of coal raw materials and hydrogen production processes, industrial hydrogen inevitably contains small amounts of impurities such as carbon monoxide, posing a serious challenge to its end-use. Therefore, large-scale purification and compression of hydrogen is a crucial link connecting hydrogen production and consumption. Proton exchange membrane hydrogen pumps (PEMHPs), due to their compact structure, low operating temperature, and lack of moving parts, show broad application prospects in hydrogen purification, electrochemical compression, and isotope separation.

[0003] The working principle of PEMHP is as follows: Crude hydrogen mixed with impurities such as carbon monoxide is introduced into the anode side, causing a hydrogen oxidation reaction (HOR). Hydrogen molecules are oxidized to generate protons and electrons. Protons migrate through the PEM to the cathode, while electrons reach the cathode through an external circuit. At the cathode, proton reduction occurs, resulting in a hydrogen evolution reaction (HER). The hydrogen mixed with impurities is purified under the drive of an external voltage. Compared with traditional hydrogen purification technologies such as pressure swing adsorption and membrane separation, PEMHP has significant advantages such as low energy consumption, simple equipment, room temperature operation, and the ability to simultaneously achieve purification and compression.

[0004] The anode is one of the core materials of PEMHP, and the anode catalyst directly determines the hydrogen conversion efficiency and tolerance to impurities. Currently, PEMHP's anode catalyst mainly uses commercial Pt / C catalysts, which are extremely sensitive to impurities such as carbon monoxide. Carbon monoxide can preferentially occupy the active sites of platinum, thereby blocking the adsorption and dissociation of hydrogen, leading to severe poisoning and deactivation of the anode catalyst.

[0005] Therefore, developing an anode and anode catalyst that combine high HOR activity, resistance to carbon monoxide poisoning, and good stability is of great significance for promoting the engineering application of PEM hydrogen pump technology. Summary of the Invention

[0006] In view of this, this application provides a proton exchange membrane hydrogen pump anode and its application. The catalyst provided in this application reduces costs while improving the activity and stability of the anode in hydrogen gas containing carbon monoxide, thereby improving the hydrogen pump's resistance to poisoning.

[0007] This application provides a proton exchange membrane hydrogen pump anode, comprising an anode plate and a catalyst composited on the anode plate.

[0008] In some specific implementations, the catalyst includes: a support and a first metal and a second metal composited on the support;

[0009] The first metal is selected from one or more of platinum, iridium, palladium and ruthenium; the second metal is selected from one or more of iron, cobalt, nickel, molybdenum and vanadium.

[0010] In some specific implementations, the mass of the first metal is 10wt% to 30wt% of the carrier mass;

[0011] The mass of the second metal is 1 wt% to 15 wt% of the carrier mass.

[0012] In some specific implementations, the molar ratio of the first metal to the second metal is 1:(0.5~20).

[0013] In some specific implementations, the first metal is platinum;

[0014] The second metal is selected from one or more of iron, cobalt, molybdenum and vanadium.

[0015] In some specific implementations, the first metal exists on the carrier in one or more of the following forms: single atom, cluster, nanoparticle, and alloy;

[0016] The second metal exists on the carrier in one or more of the following forms: single atom, cluster, nanoparticle, and alloy.

[0017] In some specific implementations, the first metal and the second metal form an alloy.

[0018] In some specific implementations, the alloy is one or more of platinum-molybdenum alloy, platinum-iron alloy, platinum-cobalt alloy, and platinum-vanadium alloy.

[0019] In some specific implementations, the carrier is a carbon carrier.

[0020] In some specific implementations, the carbon carrier includes carbon powder;

[0021] The charcoal powder is selected from one of Vulcan XC-72, Ketjenblack EC-300J, and Black Pearls 2000.

[0022] Furthermore, this application also provides a proton exchange membrane hydrogen pump, including the above-described proton exchange membrane hydrogen pump anode.

[0023] The proton exchange membrane hydrogen pump anode provided in this application includes an anode sheet and a catalyst composited on the anode sheet. The catalyst includes a support and a first metal and a second metal composited on the support. The first metal is selected from one or more of platinum, iridium, palladium, and ruthenium; the second metal is selected from one or more of iron, cobalt, nickel, molybdenum, and vanadium. The first metal and the second metal can form a synergistic structure on the support. The first metal serves as the main active center for the hydrogen oxidation reaction, and the second metal can regulate the electronic structure of the first metal, thereby reducing the adsorption of carbon monoxide at the active site or promoting its oxidative removal. This synergistic effect enables the anode containing the catalyst to maintain high hydrogen oxidation activity and stability in hydrogen fuel containing carbon monoxide, thereby improving the carbon monoxide poisoning resistance of the proton exchange membrane hydrogen pump containing the anode.

[0024] Experimental results show that the catalyst prepared in this application exhibits a performance decrease of only 2.4% under test conditions of 1000 ppm CO / H2. Attached Figure Description

[0025] Figure 1 These are scanning electron microscope (SEM) images and transmission electron microscope (TEM) images of the catalyst in Example 1, and X-ray diffraction (XRD) patterns of the catalysts in Example 1 and Comparative Example 2. 1a is a scanning electron microscope (SEM) image, 1b is a transmission electron microscope (TEM) image, and 1c is an XRD pattern.

[0026] Figure 2 This is an elemental distribution diagram of the catalyst in Example 1 under a high-resolution transmission electron microscope;

[0027] Figure 3 This is a graph showing the HOR performance of the catalyst in Example 1 in pure hydrogen and hydrogen containing carbon monoxide.

[0028] Figure 4 This is a graph showing the HOR performance of the catalyst in Example 4 in pure hydrogen and hydrogen containing carbon monoxide.

[0029] Figure 5 This is a graph showing the HOR performance of the catalyst in Example 5 in pure hydrogen and hydrogen containing carbon monoxide.

[0030] Figure 6 This is a graph showing the HOR performance of the catalyst in Example 6 in pure hydrogen and hydrogen containing carbon monoxide.

[0031] Figure 7 This is a graph showing the HOR performance of the catalyst in Comparative Example 2 in pure hydrogen and hydrogen containing carbon monoxide.

[0032] Figure 8 These are the LSV diagrams of the catalysts in Examples 1-3 and Comparative Examples 1-3 in pure hydrogen;

[0033] Figure 9The LSV diagrams are for the catalysts of Examples 1-3 and Comparative Examples 1-3 at 1000 ppm CO / H2. Detailed Implementation

[0034] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0035] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0036] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions may be performed simultaneously.

[0037] This application provides a proton exchange membrane hydrogen pump anode, comprising an anode plate and a catalyst composited on the anode plate. The proton exchange membrane hydrogen pump anode is the core functional component in the proton exchange membrane hydrogen pump where the hydrogen oxidation reaction occurs; the catalyst provides core active sites for the anode hydrogen oxidation reaction and also possesses excellent resistance to carbon monoxide poisoning, enabling the anode to maintain stable catalytic performance in hydrogen fuel containing carbon monoxide impurities.

[0038] The anode provided in this application includes an anode sheet, which serves as a support matrix for the catalyst, providing a stable and high specific surface area adhesion interface for the catalyst. This ensures that the catalyst is uniformly and firmly bonded to the anode surface, preventing catalyst deactivation due to detachment or migration during long-term operation and start-stop cycles. This application does not specifically limit the source of the anode sheet; it can be a self-made anode sheet prepared according to conventional manufacturing processes in the fuel cell field, or it can be a commercially available anode sheet used in proton exchange membrane fuel cells. In some specific implementations, the anode sheet can be one or more of carbon paper, carbon cloth, and carbon nanotube-modified carbon paper.

[0039] The anode provided in this application further includes a catalyst, which includes a support and a first metal and a second metal composited on the support; wherein the first metal is selected from one or more of platinum, iridium, palladium and ruthenium; and the second metal is selected from one or more of iron, cobalt, nickel, molybdenum and vanadium.

[0040] In this application, the catalyst comprises a first metal and a second metal. The first metal is the active center for the hydrogenation reaction, and the second metal can weaken the adsorption of carbon monoxide on the noble metal or promote the premature oxidation of carbon monoxide. In some specific implementations, the first metal is selected from one or more of platinum, iridium, palladium, and ruthenium, preferably platinum; the second metal is selected from one or more of iron, cobalt, nickel, molybdenum, and vanadium, preferably one of iron, cobalt, molybdenum, and vanadium, more preferably molybdenum; the mass of the first metal is 10wt% to 30wt% of the support mass, preferably 15wt% to 25wt%, more preferably 15wt% or 20wt%; the mass of the second metal is 1wt% to 15wt% of the support mass, preferably 3wt% to 10wt%, more preferably 5wt%, 7wt%, or 10wt%; the molar ratio of the first metal to the second metal is 1:(0.5 to 20), preferably 1:(0.5 to 18), more preferably 1:0.5, 1:1, or 1:18.

[0041] In some specific implementations, the first metal exists in the carrier in one or more of the following forms: single atom, cluster, nanoparticle, and alloy; the first metal and / or the second metal exist on the carbon carrier in one or more of the following forms: single atom, cluster, nanoparticle, and alloy; in some specific implementations, when the first metal is platinum, it is preferably alloyed with the second metal, more preferably a platinum-vanadium alloy or a platinum-molybdenum alloy.

[0042] In this application, the catalyst further includes a support, which serves as a loading substrate for the first and second metals and achieves a high degree of dispersion of the active components; in some specific implementations, the support is a carbon support; this application does not specifically limit the source of the carbon support, which can be a commercially available carbon support or a carbon support prepared by means of preparation, preferably a commercially available carbon support; in some specific implementations, the carbon support is made from carbon powder, which is selected from one of Vulcan XC-72, Ketjenblack EC-300J and Black Pearls 2000.

[0043] This application does not specifically limit the source of the catalyst. In some specific implementations, the preparation method of the catalyst includes the following steps:

[0044] 1) The catalyst precursor is obtained by mixing the support solution, the first metal precursor, and the second metal precursor, evaporating the solvent, and then obtaining the catalyst precursor.

[0045] 2) The catalyst precursor is heat-treated under a reducing atmosphere and then cooled to obtain the catalyst.

[0046] Before preparing the catalyst precursor, this application can prepare a support solution. In some specific implementations, the solution is prepared according to the following steps: mixing the support with an organic solvent to obtain the support solution; the types of support used in this application are as described above and will not be repeated here. In some specific implementations, the organic solvent is selected from one or more of ethanol, acetone, and ethylene glycol, preferably one or both of ethanol and acetone, more preferably a mixture of ethanol and acetone; the concentration of the support solution is 5 mg / mL to 15 mg / mL, preferably 8 mg / mL to 12 mg / mL, more preferably 10 mg / mL; the mixing method is preferably ultrasonic mixing, and the mixing time is 20 min to 30 min, preferably 30 min.

[0047] This application obtains a catalyst precursor by mixing the carrier solution, the first metal precursor, and the second metal precursor, and then evaporating the solvent. In some specific implementations, when the first metal is platinum, the platinum precursor is selected from one or more of chloroplatinic acid, platinum acetylacetonate, potassium chloroplatinate, sodium chloroplatinate, ammonium chloroplatinate, potassium chloroplatinate, sodium chloroplatinate, and ammonium chloroplatinate, preferably chloroplatinic acid; when the first metal is iridium, the iridium precursor is selected from one or more of chloroiridium acid, iridium chloride, iridium acetylacetonate, and iridium acetate, preferably chloroiridium acid; when the first metal is palladium, the palladium precursor is selected from one or more of palladium chloride, palladium acetylacetonate, and palladium acetate, preferably palladium chloride; when the first metal is ruthenium, the ruthenium precursor is selected from one or more of ruthenium chloride, ruthenium acetylacetonate, and ruthenium acetate, preferably ruthenium acetylacetonate; in some specific implementations... In this method, when the second metal is iron, the iron metal source is selected from one or more of ferric chloride, ferric acetylacetonate, and ferric oxalate, preferably ferric acetylacetonate; when the second metal is cobalt, the cobalt metal source is selected from one or more of cobalt chloride, cobalt acetylacetonate, and cobalt acetate, preferably cobalt acetylacetonate; when the second metal is nickel, the nickel metal source is selected from one or more of nickel chloride, nickel acetylacetonate, and nickel acetate, preferably nickel acetylacetonate; when the second metal is molybdenum, the molybdenum metal source is selected from one or more of molybdenum acetylacetonate, ammonium molybdate, and sodium molybdate, preferably molybdenum acetylacetonate; when the second metal is vanadium, the vanadium metal source is selected from one or more of vanadium chloride and vanadium acetylacetonate, preferably vanadium chloride; the molar ratio of the first metal precursor to the second metal precursor is 1:(0.5~20), preferably 1:(0.5~18), more preferably 1:0.5, 1:1, or 1:18; this application does not specifically limit the solvent of the first metal source, including but not limited to one or more of ethanol, acetone, and ethylene glycol, preferably a mixture of ethanol and acetone.

[0048] In some specific implementations, this application does not specifically limit the mixing method of the support solution, the first metal precursor, and the second metal precursor, but preferably uses ultrasonic stirring; the mixing time is 0.5h to 1.5h, preferably 1.5h; the solvent evaporation temperature is 80℃ to 150℃, preferably 100℃ to 130℃, more preferably 120℃; the solvent evaporation time is 3h to 5h, preferably 4h to 5h, more preferably 5h. In one specific implementation, the specific steps are as follows: first metal precursor solution and second metal precursor are added sequentially to carbon support, ultrasonically stirred, and then the solvent is evaporated to obtain catalyst precursor.

[0049] This application obtains the catalyst precursor by heat treatment under a reducing atmosphere, followed by cooling to obtain the anode catalyst. In some specific implementations, the reducing atmosphere is a hydrogen-argon mixture, with a hydrogen volume fraction of 1% to 5%, preferably 5%; the gas flow rate of the reducing atmosphere is 100 mL / min to 200 mL / min. The heat treatment rate is 3℃ / min to 10℃ / min, preferably 4℃ / min to 8℃ / min, more preferably 5℃ / min; the heat treatment temperature is 600℃ to 1000℃, preferably 700℃ to 900℃, more preferably 800℃; the heat treatment time is 1h to 3h, preferably 1.5h to 2.5h, more preferably 2h; the cooling rate is 3℃ / min to 10℃ / min, preferably 4℃ / min to 8℃ / min, more preferably 5℃ / min; before heat treatment, the catalyst precursor powder is ground into powder, preferably in an agate mortar; in a specific implementation, the specific steps include grinding the catalyst precursor into powder in an agate mortar and then transferring it to a corundum crucible for high-temperature treatment in a hydrogen-argon mixed atmosphere, and then cooling to obtain the catalyst.

[0050] Furthermore, this application also provides a proton exchange membrane hydrogen pump, including the above-mentioned proton exchange membrane hydrogen pump anode; in some specific implementations, the anode includes an anode plate and the above-mentioned catalyst, and the types and sources of the anode plate and catalyst are as described above, and will not be repeated here.

[0051] The proton exchange membrane hydrogen pump anode provided in this application includes an anode sheet and a catalyst composited on the anode sheet. The catalyst includes a support and a first metal and a second metal composited on the support. The first metal is selected from one or more of platinum, iridium, palladium, and ruthenium; the second metal is selected from one or more of iron, cobalt, nickel, molybdenum, and vanadium. The first metal and the second metal can form a synergistic structure on the support. The first metal serves as the main active center for the hydrogen oxidation reaction, and the second metal can regulate the electronic structure of the first metal, thereby reducing the adsorption of carbon monoxide at the active site or promoting its oxidative removal. This synergistic effect enables the anode containing the catalyst to maintain high hydrogen oxidation activity and stability in hydrogen fuel containing carbon monoxide, thereby improving the carbon monoxide poisoning resistance of the proton exchange membrane hydrogen pump containing the anode.

[0052] Experimental results show that the catalyst prepared in this application exhibits a performance decrease of only 2.4% under test conditions of 1000 ppm CO / H2.

[0053] The present application is further illustrated below with reference to embodiments. The scope of protection of the present application is not limited to the following embodiments.

[0054] Example 1

[0055] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone, and sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. 4.25 mL of a 50 mg / mL chloroplatinic acid acetone solution and 68 mg of molybdenum acetylacetonate (platinum metal content approximately 20% of the total catalyst, molybdenum metal content approximately 5% of the total catalyst, with a platinum to molybdenum molar ratio of approximately 2:1) were added sequentially to the carbon support. Sonication and stirring were alternately performed for 1.5 h to ensure sufficient metal loading. The beaker was then dried in a 120℃ oven for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after the organic solvent was evaporated, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. In a 5% hydrogen-argon mixture, the temperature was increased from room temperature to 800℃ at a rate of 5℃ / min, held for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0056] Figure 1 These are scanning electron microscope (SEM) images, transmission electron microscope (TEM) images, and X-ray diffraction (XRD) patterns of the catalyst in Example 1. 1a is the SEM image. Figure 1 As shown in a, the catalyst morphology is spherical; 1b is a transmission electron microscope image, as... Figure 1 b shows that the active metal was successfully loaded onto the carbon support; Figure 1 c is the X-ray diffraction pattern, which clearly corresponds to the (111), (200), and (220) crystal planes of platinum, confirming the successful loading of platinum; Figure 2This is the elemental distribution diagram of the catalyst in Example 1 under a high-resolution transmission electron microscope, as shown below. Figure 2 As described above, platinum and molybdenum were successfully loaded onto a carbon support and were evenly distributed.

[0057] Example 2

[0058] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone in equal volumes, and the mixture was sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. 4.37 mL of a 50 mg / mL chloroplatinic acid acetone solution and 98 mg of molybdenum acetylacetonate (platinum metal content approximately 20% of the total catalyst, molybdenum metal content approximately 7% of the total catalyst, with a platinum to molybdenum molar ratio of approximately 3:2) were added sequentially to the carbon support, and the mixture was sonicated and stirred alternately for 1.5 h to ensure sufficient metal loading. The beaker was then placed in a 120℃ oven and dried for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after the organic solvent was evaporated, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. The temperature was increased from room temperature to 800℃ at a rate of 5℃ / min in a 5% hydrogen-argon mixture, held for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0059] Example 3

[0060] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone in equal volumes, and the mixture was sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. Then, 3.19 mL of a 50 mg / mL chloroplatinic acid acetone solution and 136 mg of molybdenum acetylacetonate (approximately 15% platinum and 10% molybdenum, with a platinum to molybdenum molar ratio of approximately 3:4) were added sequentially to the carbon support. The mixture was then subjected to alternating sonication and stirring for 1.5 h to ensure sufficient metal loading. The beaker was then dried in a 120 °C oven for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after solvent evaporation, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. The temperature was increased from room temperature to 800 °C at a rate of 5 °C / min in a 5% (v / v) hydrogen-argon mixture, held at this temperature for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0061] Example 4

[0062] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone in equal volumes, and the mixture was sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. 4.25 mL of a 50 mg / mL chloroplatinic acid acetone solution and 126.48 mg of iron acetylacetone (approximately 20% platinum and 5% iron content of the total catalyst, with a platinum to iron molar ratio of approximately 1:1) were added sequentially to the carbon support. The mixture was then subjected to alternating sonication and stirring for 1.5 h to ensure sufficient metal loading. The beaker was then dried in a 120°C oven for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after the organic solvent was evaporated, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. The temperature was increased from room temperature to 800°C at a rate of 5°C / min in a 5% (v / v) hydrogen-argon mixture, held at this temperature for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0063] Example 5

[0064] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone in equal volumes, and the mixture was sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. 4.25 mL of a 50 mg / mL chloroplatinic acid acetone solution and 120.9 mg of cobalt acetylacetonate (approximately 20% platinum and 5% cobalt, with a platinum to cobalt molar ratio of approximately 1:1) were added sequentially to the carbon support, and the mixture was sonicated and stirred alternately for 1.5 h to ensure sufficient metal loading. The beaker was then dried in a 120 °C oven for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after the organic solvent was evaporated, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. The temperature was increased from room temperature to 800 °C at a rate of 5 °C / min in a 5% (v / v) hydrogen-argon mixture, held for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0065] Example 6

[0066] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone, and sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. 4.25 mL of a 50 mg / mL chloroplatinic acid acetone solution and 61.76 mg of vanadium chloride (approximately 20% platinum and 5% vanadium, with a platinum to vanadium molar ratio of approximately 1:1) were added sequentially to the carbon support, and the mixture was sonicated and stirred alternately for 1.5 h to ensure sufficient metal loading. The beaker was then dried in a 120°C oven for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after solvent evaporation, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. The temperature was increased from room temperature to 800°C at a rate of 5°C / min in a 5% (v / v) hydrogen-argon mixture, held for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0067] Comparative Example 1

[0068] This comparative example uses a commercially available Pt / C catalyst with a platinum content of 20%, manufactured by Suzhou Shengernuo Technology Co., Ltd., model SENPT20X.

[0069] Comparative Example 2

[0070] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone, and sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. 3.98 mL of a 50 mg / mL chloroplatinic acid acetone solution (approximately 20% platinum metal content of the total catalyst) was added to the carbon support, and sonication and stirring were alternately performed for 1.5 h to ensure sufficient metal loading. The beaker was then dried in a 120℃ oven for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after the organic solvent was evaporated, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. In a 5% (v / v) hydrogen-argon mixture, the temperature was increased from room temperature to 800℃ at a rate of 5℃ / min, held for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0071] Figure 1 c is the X-ray diffraction pattern of Comparison 2, derived from... Figure 1 c clearly corresponds to the (111), (200), and (220) crystal planes of platinum, confirming the successful loading of platinum.

[0072] Comparative Example 3

[0073] 300 mg of carbon powder was added to a beaker containing 30 mL of a mixture of ethanol and acetone in equal volumes, and the mixture was sonicated for 30 min to ensure homogeneity, thus obtaining a carbon support. 4.25 mL of a 50 mg / mL chloroplatinic acid acetone solution and 78.83 mg of ruthenium acetylacetone (approximately 20% platinum and 5% ruthenium, with a platinum to ruthenium molar ratio of approximately 2:1) were added sequentially to the carbon support, and the mixture was sonicated and stirred alternately for 1.5 h to ensure sufficient metal loading. The beaker was then dried in a 120°C oven for 5 h to ensure complete evaporation of the organic solvent. The catalyst precursor, after the organic solvent was evaporated, was ground into powder using an agate mortar and transferred to a corundum crucible for high-temperature treatment. The temperature was increased from room temperature to 800°C at a rate of 5°C / min in a 5% (v / v) hydrogen-argon mixture, held for 2 h, and then cooled to room temperature at the same rate to obtain a catalyst resistant to carbon monoxide poisoning.

[0074] Electrochemical performance testing:

[0075] 1) Rotating disk electrode test:

[0076] Weigh 5 mg of the catalysts prepared in Examples 1, 4-6, and Comparative Example 2 into centrifuge tubes, respectively. Transfer 1 mL of anhydrous ethanol and 20 μL of 5% Nafion solution, and sonicate for 1 h to disperse them evenly to obtain a catalyst slurry. Polish a 5 mm diameter glassy carbon electrode, wipe it clean, and drop 10 μL of the catalyst slurry onto the glassy carbon electrode. Let it air dry for later use.

[0077] The prepared working electrode was placed in a 0.05 M H₂SO₄ electrolyte for electrochemical testing. The electrolyte was kept saturated with hydrogen gas. Electrochemical activation was first performed, with 20 cycles at a scan rate of 0.05 V / s within a voltage range of -0.4 to -0.4 V, while maintaining the rotating disk electrode speed at 2500 rpm. The activated working electrode was then subjected to CV testing under hydrogen saturation, with a scan rate of 0.005 V / s within a voltage range of -0.4 to -0.4 V, thus obtaining the HOR performance of the catalyst in pure hydrogen. The voltages mentioned above are relative to the reversible hydrogen electrode and require IR correction.

[0078] The test conditions for the resistance to carbon monoxide poisoning were as follows: 1000, 2000, and 10000 ppm CO / H2 were introduced into the electrolyte until saturation. The activated working electrode was subjected to CV testing. The HOR performance of the catalyst in hydrogen gas containing carbon monoxide was obtained within a voltage range of -0.4 to -0.8 V and a scan rate of 0.005 V / s.

[0079] 2) Membrane electrode testing:

[0080] 60 mg of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 were weighed and placed in a ball mill jar. 0.6 g of zirconia grinding balls with a diameter of 3 mm, 1.8 g of zirconia grinding balls with a diameter of 2 mm, and 0.3 g of water were added for ball milling. The catalyst was completely dispersed in a mixed solvent of isopropanol and water (volume ratio 3:1) for 20 mL, and 0.24 g of 5% Nafion solution was added. The mixture was ultrasonically dispersed for 1 h to obtain a catalyst slurry. The dispersed catalyst slurry was sprayed onto a PEM (Nafion 212) with a spray area of ​​5 × 5 cm (effective area of ​​2 × 2 cm). The anode catalyst loading was 1 mg / cm². The cathode catalyst, a commercial Pt / C catalyst with a loading of 0.5 mg / cm², was sprayed onto the other side of the PEM. The catalyst-coated PEM was then hot-pressed to reduce the interfacial resistivity.

[0081] A hydrogen pump assembly consisting of a catalyst-coated PEM and a gas diffusion layer (carbon paper) was used for membrane electrode testing. At 60°C, pure water was circulated on the cathode side, while pure hydrogen and hydrogen gas containing carbon monoxide were introduced on the anode side. The gas flow rate was controlled at 50 ccm, and linear sweep voltammetry (LSV) was performed within a voltage range of 0V to 1V.

[0082] 3) Test results:

[0083] Figures 3-6 The figures show the HOR performance of the catalysts in Examples 1, 4, 5, and 6 in pure hydrogen and hydrogen containing carbon monoxide. By comparing the HOR performance in pure hydrogen and hydrogen containing carbon monoxide, it can be seen that the increase in current at 0.2 V in hydrogen containing carbon monoxide in Examples 1 and 4-6 indicates the premature oxidation of carbon monoxide and that they have excellent resistance to carbon monoxide poisoning. Figure 7 The above is a graph showing the HOR performance of the catalyst in Comparative Example 2 in pure hydrogen and hydrogen containing carbon monoxide, as shown. Figure 7 As shown, compared with the bimetallic catalyst, the platinum catalyst in Comparative Example 2 exhibits a significant decrease in resistance to carbon monoxide poisoning.

[0084] Figure 8 These are the LSV diagrams of the catalysts in Examples 1-3 and Comparative Examples 1-3 in pure hydrogen; Figure 9 These are the LSV diagrams of the catalysts in Examples 1-3 and Comparative Examples 1-3 at 1000 ppm CO / H2. Figure 8 and Figure 9 As shown, compared with the single platinum catalysts of Comparative Examples 1 and 2 and the conventional platinum-ruthenium catalyst of Comparative Example 3 which has good resistance to carbon monoxide poisoning, the catalysts of Examples 1-3 have excellent hydrogen hydration and resistance to carbon monoxide poisoning.

[0085] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and application concept of this application, should be included within the scope of protection of this application.

Claims

1. A proton exchange membrane hydrogen pump anode, characterized in that, Includes an anode plate and a catalyst composited on the anode plate; The catalyst includes a support and a first metal and a second metal composited on the support; The first metal is selected from one or more of platinum, iridium, palladium and ruthenium; the second metal is selected from one or more of iron, cobalt, nickel, molybdenum and vanadium.

2. The anode according to claim 1, characterized in that, The mass of the first metal is 10wt% to 30wt% of the carrier mass; The mass of the second metal is 1 wt% to 15 wt% of the carrier mass.

3. The anode according to claim 1, characterized in that, The molar ratio of the first metal to the second metal is 1:(0.5~20).

4. The anode according to claim 2, characterized in that, The first metal is platinum; The second metal is selected from one or more of iron, cobalt, molybdenum and vanadium.

5. The anode according to any one of claims 1 to 4, characterized in that, The first metal exists on the carrier in one or more of the following forms: single atom, cluster, nanoparticle, and alloy; The second metal exists on the carrier in one or more of the following forms: single atom, cluster, nanoparticle, and alloy.

6. The anode according to any one of claims 5, characterized in that, The first metal and the second metal form an alloy.

7. The anode according to any one of claims 6, characterized in that, The alloy is one or more of the following: platinum-molybdenum alloy, platinum-iron alloy, platinum-cobalt alloy, and platinum-vanadium alloy.

8. The anode according to claim 1, characterized in that, The carrier is a carbon carrier.

9. The anode according to claim 8, characterized in that, The carbon carrier includes carbon powder; The charcoal powder is selected from one of Vulcan XC-72, Ketjenblack EC-300J, and Black Pearls 2000.

10. A proton exchange membrane hydrogen pump, characterized in that, Includes the proton exchange membrane hydrogen pump anode as described in any one of claims 1 to 9.

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