A fuel cell anode catalyst resistant to poisoning and a method for preparing the same, and a fuel cell

Abstract

The present application provides a kind of fuel cell anode catalyst of anti-poisoning and its preparation method, fuel cell, catalyst includes carrier and the alloy nanoparticle cluster supported on carrier;Alloy nanoparticle cluster includes ruthenium, platinum and optional third metal;Third metal is one or more selected from palladium, molybdenum, cobalt, tin, tungsten;The particle size of alloy nanoparticle cluster is 1-2.5nm.The fuel cell anode catalyst of the present application is that ruthenium, platinum and optional third metal form alloy nanoparticle cluster with particle size of 1-2.5nm, platinum oxygen coordination number is greater than 2, i.e.high platinum oxygen coordination, significantly reduce the adsorption capacity between platinum and carbon monoxide, phosphoric acid, hydrogen sulfide, ammonia and other toxic substances, the anti-poisoning capacity of fuel cell anode catalyst is greatly improved, can be stably worked in the anode fuel gas (such as hydrogen) containing high concentration CO (such as 100-1000ppm CO).

Description

[0001] This application claims priority to Chinese Patent Application No. 202410619876.8, filed on May 17, 2024, entitled “An Anti-poisoning Fuel Cell Anode Catalyst and Its Preparation Method and Fuel Cell”, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0002] The present application relates to the technical field of fuel cells, in particular to an anti-poisoning fuel cell anode catalyst and its preparation method and fuel cell. BACKGROUND

[0003] A fuel cell is a new type of sustainable, efficient and environmentally friendly energy conversion device. Fuel cells can directly convert the chemical energy of fuel into electrical energy. Hydrogen is the fuel used by the anode of a fuel cell, and currently hydrogen is mainly obtained from the reforming of natural gas and the conversion of small organic molecules, which inevitably contains a certain concentration of toxic substances, including carbon monoxide, hydrogen sulfide and ammonia. The toxic substances in the fuel can seriously poison the anode catalyst in the fuel cell, therefore, how to improve the tolerance of the anode catalyst to toxic substances is of great significance to the practical application of fuel cells. In addition, phosphoric acid electrolyte high-temperature proton exchange membrane fuel cells have great application prospects due to their high efficiency and stronger tolerance, however, they are easily poisoned by phosphoric acid, therefore, it is crucial to improve the tolerance of the catalyst to phosphoric acid poisoning.

[0004] Anode anti-poisoning catalysts are mainly divided into two types, the first type is Pt-based alloy catalyst, and the second type is Pt and WO2, MoO2, TiO2, etc. oxide composite materials. CO interacts very strongly with the surface of noble metal Pt, and 100 ppm of CO impurities in hydrogen fuel can quickly poison the surface, causing the anode catalyst to be inactivated. In order to improve the anti-poisoning ability, the introduction of a second metal or metal oxide on the surface helps to assist in the formation of hydroxyl radicals at a lower potential, and the highly active hydroxyl radicals can oxidize and remove the CO adsorbed on the Pt surface. On the other hand, the second metal can change the electronic properties of the metal Pt surface to some extent, thereby weakening the interaction force between the toxic species CO and the surface.

[0005] Chinese patent CN1418725A used in-situ chemical reduction homogeneous deposition method to prepare carbon nanotube supported PtRu, PtSn, PtRuSn and other alloy anti-poisoning catalysts. Chinese patent CN101436669A used CO2 supercritical fluid to deposit metal organic compounds onto conductive carriers, and then reduced to obtain 1-4 nm Pt-M alloy anti-CO poisoning catalysts. Chinese patent CN1832234A used wet chemical method to synthesize PtAu nanocatalysts supported on oxides as anti-CO poisoning catalysts for fuel cell applications. US patent US6007934A, Emmanuel Auer et al. used low-temperature liquid formaldehyde to stepwise or simultaneously reduce Pt salt and Ru salt, and then low-temperature drying method to prepare carbon-supported catalysts containing both metal Pt and Ru, and the two metals exist in a non-alloy state but are highly dispersed on the support carbon, which has better anti-CO poisoning performance than commercial PtRu / C catalysts. US patent US5939220A, Alec Gordon Gunner et al. used liquid-phase deposition method to prepare PtCoMo / C ternary alloy catalysts as anode catalysts for proton exchange membrane fuel cells, which have certain anti-CO poisoning performance. Based on the existing technology, it can be seen that the current anti-CO poisoning hydrogen oxidation catalysts are still mainly based on Pt-based metal alloy catalysts, and the anti-poisoning ability is limited. According to the literature Ehteshami S.M.M.;Jia Q,;Halder A.;Chan S.H.;Mukerjee S. Electrochimica Acta 2013, 107, 155, it can be seen that the platinum-based alloy catalysts in the existing research still cannot meet the demand of anti-CO poisoning in fuel cells, and 20 ppm of CO in the fuel can cause more than 50% loss of activity of various platinum-based alloy catalysts within 1 h.

[0006] The existing fuel cell anode Pt catalyst is poisoned by the fuel poisoning substances, which causes large voltage loss, and often cannot effectively protect the catalyst to work stably in the anode fuel gas containing CO with a concentration of more than 100 ppm, and also cannot present high catalytic activity in the high-temperature proton exchange membrane fuel cell system with phosphoric acid as electrolyte. Therefore, how to find a fuel cell anode catalyst that can work stably in fuel gas containing relatively high concentration of CO and other poisoning substances, and can present high catalytic performance in the high-temperature proton exchange membrane fuel cell with phosphoric acid as electrolyte is a technical problem to be solved at present. SUMMARY

[0007] In view of the above problems, the present application provides an anti-poisoning fuel cell anode catalyst and a preparation method thereof, and a fuel cell.

[0008] In one aspect, the present application provides a fuel cell anode catalyst with resistance to poisoning, wherein the catalyst comprises a support and alloy nanoparticle clusters supported on the support; the alloy nanoparticle clusters comprise ruthenium, platinum and optionally a third metal; the third metal is one or more selected from the group consisting of palladium, molybdenum, cobalt, tin and tungsten; and the alloy nanoparticle clusters have a particle size of 1-2.5 nm.

[0009] In another aspect, the present application provides a method for preparing the fuel cell anode catalyst as described above, wherein the method comprises the following steps:

[0010] (1) providing a basic dispersion liquid A comprising a first polyol and a support and dissolved with a ruthenium precursor;

[0011] (2) introducing carbon monoxide into the dispersion liquid A in step (1) and performing a first heating reflux to obtain a dispersion liquid B;

[0012] (3) dissolving a platinum precursor and optionally a third metal precursor in a second polyol to obtain a solution C;

[0013] (4) adding the solution C from step (3) into the dispersion liquid B from step (2) and performing a second heating reflux, and then performing a solid-liquid separation to obtain the fuel cell anode catalyst.

[0014] In still another aspect, the present application provides a fuel cell, wherein the anode of the fuel cell comprises the fuel cell anode catalyst with resistance to poisoning as described above, or comprises the fuel cell anode catalyst with resistance to poisoning prepared by the method as described above.

[0015] The fuel cell is a proton exchange membrane fuel cell or a phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell.

[0016] Advantages:

[0017] (1) In the fuel cell anode catalyst of the present application, ruthenium, platinum and optionally a third metal form alloy nanoparticle clusters with a particle size of 1-2.5 nm, and the platinum has a coordination number greater than 2, i.e. high platinum coordination, which significantly reduces the adsorption capacity between platinum and poisoning substances such as carbon monoxide, phosphoric acid, hydrogen sulfide and ammonia, and greatly improves the resistance to poisoning of the fuel cell anode catalyst, so that the fuel cell anode catalyst can work stably in an anode fuel gas (such as hydrogen) containing high concentration of CO (such as 100-1000 ppm CO);

[0018] (2) The fuel cell anode catalyst of the present application can reduce the adsorption poisoning of phosphoric acid on the active sites of the catalyst, thereby improving the performance of a high-temperature proton exchange membrane fuel cell using phosphoric acid as the electrolyte;

[0019] (3) When the fuel cell anode catalyst of the present invention is used in fuel cells that use impure hydrogen containing poisoning substances such as hydrogen sulfide and ammonia as anode fuel, it can significantly reduce the voltage loss caused by poisoning during battery operation and significantly improve the working stability.

[0020] (4) When the fuel cell anode catalyst of the present invention is used in a fuel cell that uses simply purified reformed gas as anode fuel, it can significantly reduce the voltage loss caused by poisoning during battery operation and significantly improve the working stability. Attached Figure Description

[0021] Figure 1 This is a transmission electron microscopy (TEM) characterization image of the catalyst synthesized in Example 1 of this invention;

[0022] Figure 2 This is the synchrotron radiation X-ray absorption spectrum of the catalyst synthesized in Example 1 of the present invention;

[0023] Figure 3 The catalysts used in Example 1 and Comparative Example 1 were respectively used as anode catalysts and maintained at 1 A·cm in a hydrogen atmosphere containing 200 ppm CO + 2% O2. -2 Stability test results against CO poisoning under constant current discharge;

[0024] Figure 4 The polarization curves and power density-current density curves of the catalyst synthesized in Example 2 and Comparative Example 2 of this invention are shown.

[0025] Figure 5 In Example 3 of this invention, the synthesized catalyst was used as the anode catalyst and maintained at 1 A·cm in a hydrogen atmosphere containing 5 ppm NH3. -2 Graphs showing the stability test results against NH3 poisoning under constant current discharge.

[0026] Figure 6 In Example 4 of this invention, the synthesized catalyst was used as the anode catalyst and maintained at 1 A·cm in a hydrogen atmosphere containing 1 ppm H2S. -2 Graph of H2S poisoning stability test under constant current discharge. Detailed Implementation

[0027] The present application will now be described in further detail with reference to the accompanying drawings and embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0028] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments. Although various aspects of embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated otherwise.

[0029] In the present application, the term "optional", "optionally" or "optionally" means that the subsequent described event or situation can occur or can not occur, and the description includes the occurrence of the event or situation and the non-occurrence of the event or situation.

[0030] In addition, the technical features involved in the different embodiments of the present application described below can be combined with each other as long as there is no conflict.

[0031] In one aspect, the present application provides an anti-poisoning fuel cell anode catalyst, comprising a carrier and an alloy nanoparticle cluster supported on the carrier; the alloy nanoparticle cluster comprises ruthenium, platinum and an optional third metal; the third metal is one or more selected from palladium, molybdenum, cobalt, tin, tungsten; the particle size of the alloy nanoparticle cluster is 1-2.5 nm.

[0032] The fuel cell anode catalyst of the present application comprises a carrier and an active component supported on the carrier, and the active component is an alloy nanoparticle cluster composed of ruthenium, platinum and an optional third metal. Importantly, the particle size of the alloy nanoparticle cluster composed of ruthenium, platinum and an optional third metal in the fuel cell anode catalyst of the present application is small, specifically 1-2.5 nm. The anode catalyst not only has good hydrogen oxidation catalytic activity, but also has high resistance to toxic substances such as carbon monoxide, hydrogen sulfide and ammonia in the anode fuel gas.

[0033] In one embodiment of the above-mentioned fuel cell anode catalyst of the present application, at least part of the platinum atoms are coordinated with oxygen, and the platinum oxygen coordination number is greater than 2, preferably 3-5.

[0034] The particle size of the fuel cell anode catalyst in the prior art is often large (such as 3-5 nm), the surface platinum valence state is low, the platinum metal coordination number with oxygen is low, and it basically mainly exists in the form of platinum-platinum metal coordination. The present application constructs a 1-2.5 nm cluster type platinum-based noble metal catalyst with high platinum oxygen coordination number, which significantly enhances the resistance of platinum to toxic substances (such as carbon monoxide, phosphoric acid, hydrogen sulfide, ammonia, etc.) in the anode fuel gas while maintaining the hydrogen oxidation activity. Specifically, in the fuel cell anode catalyst of the present application, most of the platinum atoms are coordinated with oxygen, or in other words, platinum is dominated by platinum atom-oxygen coordination, and the platinum oxygen coordination number, i.e. the number of oxygen atoms coordinated with one platinum atom, is greater than 2, preferably 3-5. In this way, when catalyzing the hydrogen oxidation reaction, the platinum is more comprehensively protected by oxygen due to the high oxygen coordination, and thus the adsorption capacity of platinum to toxic substances such as carbon monoxide, hydrogen sulfide and ammonia is greatly weakened, so that the anti-poisoning performance of the catalyst is significantly improved, but small molecules of hydrogen can easily contact, adsorb and react with platinum, and the particle size of the alloy nanoparticle cluster is small, so it has a larger catalytic area, making the catalyst have very good hydrogen oxidation catalytic activity.

[0035] In another embodiment of the fuel cell anode catalyst of the present application, the loading of ruthenium in the fuel cell anode catalyst is 1% to 30%; and / or

[0036] the loading of platinum in the fuel cell anode catalyst is 1% to 60%; and / or

[0037] the loading of the third metal in the fuel cell anode catalyst is 1% to 30%.

[0038] Further, in the fuel cell anode catalyst of the present application, the loading of ruthenium, platinum and the third metal in the total mass of the catalyst can also be 5% to 60%, and the sum of the loading of ruthenium, platinum and the third metal and the loading of the carrier is 100%. Specifically, the loading of ruthenium in the fuel cell anode catalyst can be 3%, 5%, 8%, 10%, 15%, 20%, 25%, etc., the loading of platinum in the fuel cell anode catalyst can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, etc., and the loading of the third metal in the fuel cell anode catalyst can be 3%, 5%, 10%, 15%, 20%, 25%. By controlling the loading of ruthenium, platinum and the third metal as above, the catalytic activity and the resistance to poisoning of the catalyst can be further improved.

[0039] On the other hand, the present application also provides a method for preparing the fuel cell anode catalyst as above, comprising the following steps:

[0040] (1) providing a basic dispersion liquid A comprising a first polyol, a carrier and dissolved therein a ruthenium precursor;

[0041] (2) passing carbon monoxide into the dispersion liquid A in step (1) and performing a first heating reflux to obtain a dispersion liquid B;

[0042] (3) dissolving a platinum precursor and optionally a third metal precursor in a second polyol to obtain a solution C;

[0043] (4) adding the solution C from step (3) dropwise into the dispersion liquid B from step (2) and performing a second heating reflux, and then performing solid-liquid separation to obtain the fuel cell anode catalyst.

[0044] In the preparation method of the present application, the ruthenium precursor and the carrier can be added together into the first polyol for dissolution and dispersion respectively to obtain a dispersion liquid; or the ruthenium precursor can be added into the first polyol for dissolution and then the carrier is added for dispersion to obtain a dispersion liquid; or the carrier can be dispersed in the first polyol first and then the ruthenium precursor is added for dissolution to obtain a dispersion liquid. Then the dispersion liquid is adjusted to be basic using a lye to obtain the dispersion liquid A as above.

[0045] In the preparation method of the present application, first, a dispersion solution of basic polyol is prepared, then carbon monoxide is introduced to induce and reduce the ruthenium, so that the ruthenium is reduced and grown on the carrier to form ultra-small ruthenium nanocrystals (metallic nanoparticles), then a polyol solution formed by dropwise adding a platinum precursor and an optional third metal precursor is added, the polyol can reduce the platinum and the optional third metal to form alloy nanoparticle clusters with ultra-small particle size together with the ruthenium. The steps of the above method of the present application are mutually coordinated and synergistic, forming alloy nanoparticle clusters with small particle size and in a certain range. The alloy nanoparticle clusters have high surface activity of platinum, which is easy to combine with oxygen in the air or water vapor to form high platinum-oxygen coordination.

[0046] In summary, the method of the present application not only forms alloy nanoparticle clusters with a particle size of 1-2.5 nm, but also has more oxygen coordinated with platinum, forming high platinum-oxygen coordination, that is, the number of oxygen atoms coordinated with one platinum atom is greater than 2, preferably 3-5. The fuel cell anode catalyst prepared by the method of the present application significantly improves the poisoning resistance of the catalyst while maintaining high activity of hydrogen oxidation. The performance and stability of the fuel cell anode using fuel gas containing toxic substances (carbon monoxide, hydrogen sulfide, ammonia, etc.) are significantly improved, and the performance of the phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell is also significantly improved.

[0047] In an embodiment of the above method of the present application, in step (1), the ruthenium precursor is one or more selected from the group consisting of ruthenium acetate, ruthenium trichloride trihydrate, ruthenium trichloride, and ruthenium acetylacetonate; and / or

[0048] The carrier is one or more selected from the group consisting of a carbon carrier, an inorganic oxide carrier, an inorganic nitride carrier, and an inorganic carbide carrier; the carbon carrier is one or more selected from the group consisting of porous carbon and mesoporous carbon; and / or

[0049] The mass ratio of the ruthenium precursor to the first polyol is (0.0001-0.1):1, and the mass ratio of the carrier to the first polyol is (0.0001-0.1):1.

[0050] In the preparation method of the present application, the above-mentioned ruthenium precursor and carrier are selected, and the mass ratio of the ruthenium precursor to the first polyol and the mass ratio of the carrier to the first polyol are controlled as above, so that the alloy nanoparticle cluster fuel cell anode catalyst with small particle size can be better prepared, the platinum can better form high platinum-oxygen coordination, and the catalyst has good anti-poisoning ability and catalytic activity. Further, the above-mentioned carbon carrier is preferably mesoporous carbon with high specific surface area, and the larger specific surface area is beneficial to the loading of small particles.

[0051] In one embodiment of the above-mentioned method of the present application, the pH value of the dispersion liquid A in step (1) is 8-11.5.

[0052] It should be noted that the ruthenium precursor and the carrier can be added (or added one after another) into the first polyhydric alcohol to obtain the dispersion liquid, and then the pH value of the dispersion liquid is adjusted to be within the above-mentioned range by adding a lye such as a sodium hydroxide solution, a potassium hydroxide solution, etc. By controlling the pH value of the dispersion liquid A as above and then carrying out the step (2) of passing carbon monoxide and the first heating reflux, it is beneficial to better form the ultra-fine ruthenium nanocrystals, and then to form the alloy nanoparticle clusters with smaller particle size in the subsequent step, so as to be beneficial to form a higher platinum-oxygen coordination number, and further to prepare the fuel cell anode catalyst with better hydrogen oxidation catalytic activity and anti-poisoning ability.

[0053] In another embodiment of the above-mentioned method of the present application, the flow rate of the carbon monoxide passed in step (2) is 0.1-500 mL / min, preferably 5-10 mL / min; and / or

[0054] The first heating reflux is carried out at 80-120℃ for 2-4h; and / or

[0055] The step (2) further comprises the following step before passing the carbon monoxide:

[0056] The dispersion liquid A is sealed and purged with an inert gas.

[0057] It should be noted that the passing of the carbon monoxide gas can be carried out at the above-mentioned fixed low flow rate, and by controlling the flow rate of the carbon monoxide passed, the temperature and time of the first heating reflux, etc. as above, it is beneficial to better form the ultra-fine ruthenium nanocrystals, and then to form the alloy nanoparticle clusters with small particle size in the subsequent step, so as to further improve the catalytic activity and anti-poisoning ability of the prepared catalyst. The inert gas used for purging can be argon.

[0058] In still another embodiment of the above-mentioned method of the present application, the platinum precursor in step (3) is one or more selected from chloroplatinic acid hexahydrate, platinum tetrachloride, potassium chloroplatinate, sodium hexahydroxy platinic acid, potassium hexahydroxy platinic acid;

[0059] The third metal precursor comprises one or more of chlorides, nitrates, sulfates of the third metal, and is preferably one or more selected from palladium chloride, phosphomolybdic acid, cobalt chloride, tin chloride; and / or

[0060] The first polyhydric alcohol and the second polyhydric alcohol are each independently selected from C2-C8 dihydric and / or trihydric alcohols, and are preferably one or more selected from ethylene glycol, propylene glycol, glycerol, triethylene glycol; and / or

[0061] The total mass ratio of the platinum precursor and the third metal precursor to the second polyol is (0.0001 to 0.1):1.

[0062] It should be noted that by selecting the above-mentioned platinum precursor, third metal precursor, and the above-mentioned first and second polyols, the method of the present invention can prepare fuel cell anode catalysts with smaller alloy nanoparticle clusters and more uniform dispersion, and higher platinum-oxygen coordination number. When the anode fuel gas contains poisoning substances, the catalyst can maintain high activity for a longer period of time, and the battery can maintain a high stable voltage operation time significantly extended.

[0063] In one embodiment of the above method of the present invention, the second heating reflux in step (4) is carried out at 150-200°C for 2-5 hours.

[0064] By controlling the temperature and time of the second heating reflux as described above, platinum and the third metal can better form small alloy nanoparticle clusters with ultra-small ruthenium nanocrystals, and platinum is coordinated with more oxygen, further improving the catalyst's anti-poisoning performance.

[0065] In one embodiment of the method described above, step (4) further includes washing, vacuum drying and grinding after the solid-liquid separation.

[0066] In another aspect, the present invention also provides a fuel cell, wherein the anode comprises the above-mentioned resistant fuel cell anode catalyst, or comprises the resistant fuel cell anode catalyst prepared by the above method;

[0067] The fuel cell is a proton exchange membrane fuel cell or a phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell.

[0068] It should be noted that, in the preparation of fuel cells, the poison-resistant fuel cell anode catalyst can first be mixed with Nafion solution, water, and organic solvent to form ink, and then the ink is sprayed onto one side of the proton exchange membrane, while the other side is sprayed with a commercial platinum-carbon catalyst used as the cathode catalyst, and then assembled into a proton exchange membrane fuel cell; or the ink can be sprayed onto the microporous layer of one gas diffusion layer, while the microporous layer of another gas diffusion layer is sprayed with a commercial platinum-carbon catalyst used as the cathode catalyst, and then assembled into a phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell.

[0069] Specifically, in proton exchange membrane fuel cells, the platinum loading at the anode can be 0.025–0.2 mg / cm³. 2 Specifically, it can be 0.05 mg / cm³. 2 0.1 mg / cm 2 The platinum loading at the cathode can be 0.2–0.6 mg / cm³. 2 Specifically, it can be 0.3 mg / cm³.2 0.4 mg / cm 2 etc. In the phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell, the anode platinum load can be 0.1-0.5 mg / cm 2 , specifically 0.2 mg / cm 2 , 0.3 mg / cm 2 , 0.4 mg / cm 2 , etc.; the cathode platinum load can be 0.5-1 mg / cm 2 , specifically 0.6 mg / cm 2 , 0.7 mg / cm 2 , 1 mg / cm 2 , etc.

[0070] The present application is further illustrated in detail by the following examples, but the present application is not limited thereto. In the following examples, the experimental instruments and raw materials involved are commercially available products, unless otherwise specified.

[0071] The reagent information used in the following examples is shown as follows:

[0072] The carbon carrier is mesoporous carbon, which is purchased from Shoua-Do, Japan, and is Ketjen Black EC-300J;

[0073] The commercial platinum-carbon catalyst is Hispec 4000 purchased from Johnson Matthey;

[0074] The gas diffusion layer is 3620 purchased from Ballard;

[0075] The high-temperature proton exchange membrane is AM-40 purchased from Fumapem, Fuma;

[0076] The proton exchange membrane is a 15-μm-thick proton exchange membrane purchased from Gore.

[0077] Example 1

[0078] 50 mg of ruthenium acetate and 80 mg of carbon carrier were dissolved and dispersed in 200 mL of ethylene glycol with ultrasonic stirring for 2 h, and the pH value was adjusted to 8 with a sodium hydroxide solution to obtain dispersion liquid A.

[0079] After sealing the dispersion liquid A, argon was blown, and then carbon monoxide was slowly introduced at a flow rate of 5 mL / min, and it was placed in an oil bath at 80°C for reflux, and after 2 h of reaction, a black ink-like viscous dispersion liquid B was obtained.

[0080] 100 mg of chloroplatinic acid hexahydrate was dissolved in 100 mL of ethylene glycol with heating and stirring to obtain solution C.

[0081] The solution C was added dropwise to the dispersion B, and heated to reflux at 180℃ for 2h. The sample was filtered and washed with water, ethanol, acetone, and dried in a vacuum desiccator. The sample was ground in a mortar. The PtRu nanoparticles with 2nm in size and high Pt oxidation number were obtained.

[0082] Figure 1 The TEM image of the PtRu alloy catalyst supported on carbon support prepared in Example 1, Figure 1 It can be seen from the TEM image that the size of the nanocluster particles is about 2nm, and the particles are uniformly distributed.

[0083] The prepared catalyst was tested by inductively coupled plasma optical emission spectrometry (ICP-OES), and the mass percentage of Pt element in the prepared catalyst was 28.18%, and the mass percentage of Ru element was 12.53%.

[0084] Figure 2 The synchrotron X-ray absorption spectrum of the PtRu alloy catalyst supported on carbon support prepared in Example 1, Figure 2 It can be seen from the TEM image that the size of the nanocluster particles is about 2nm, and the particles are uniformly distributed.

[0085] The prepared catalyst was prepared into ink for fuel cell test, and the ink composition was: catalyst 20mg, 5wt% Nafion solution 0.5mL, solvent water and isopropanol each 4mL; the ink was placed in an ice water bath and ultrasonicated until uniformly dispersed; the prepared ink was uniformly sprayed on one side of Gore 15μm thick proton exchange membrane to form an anode, and the other side was sprayed with commercial platinum carbon catalyst Hispec4000 to form a cathode. The proton exchange membrane with catalyst sprayed thereon was placed in a fuel cell test fixture for fuel cell test, and the platinum loading of the anode was 0.1mg / cm 2 , and the platinum loading of the cathode was 0.4mg / cm 2 .

[0086] The fuel cell was operated under hydrogen-air conditions (hydrogen at the anode and air at the cathode) at 80°C and at 0–4 A·cm. -2 Polarization curves are obtained by constant current step transitions between the curves, and the test is repeated until the curves coincide.

[0087] The fuel cell is controlled at 1A·cm -2 A constant current discharge was applied, and the initial potential was obtained after the curve stabilized. Then, the anode fuel gas, pure hydrogen, was switched to a hydrogen atmosphere containing 200 ppm CO + 2% O2, maintained at 1 A·cm throughout the process. -2 The hydrogen oxidation stability test was conducted under constant current discharge, and the test results are as follows: Figure 3 As shown. By Figure 3 It can be seen that the prepared catalyst can maintain high activity for a long time in a hydrogen atmosphere of 200ppm CO + 2% O2, and the battery voltage drops by only 30mV over a long period of time, with the voltage basically not decaying over a long period of time.

[0088] Example 2

[0089] Dissolve and disperse 50 mg of ruthenium trichloride trihydrate and 100 mg of carbon support in 50 mL of ethylene glycol, sonicate for 2 h, and adjust the pH to 10 with sodium hydroxide solution to obtain dispersion A.

[0090] After sealing dispersion A, it was purged with argon gas, and then carbon monoxide was slowly introduced at a flow rate of 10 mL / min. The mixture was then placed in an oil bath and refluxed at 120 °C. After reacting for 2 hours, a black ink-like viscous dispersion B was obtained.

[0091] Solution C was obtained by dissolving 80 mg platinum tetrachloride and 20 mg palladium chloride in 100 mL ethylene glycol by heating and stirring.

[0092] Solution C was added dropwise to dispersion B, and the mixture was heated under reflux at 180°C for 2 hours. After filtration, the sample was washed by centrifugation with water, ethanol, and acetone, dried under vacuum, and then ground into a fine powder using a mortar and pestle. This yielded 2 nm clustered platinum-ruthenium-palladium nanoparticles loaded on a carbon support.

[0093] The obtained catalyst was formulated into an ink for fuel cell testing. The ink composition was: 20 mg of catalyst, 0.5 mL of 5 wt% Nafion solution, and 4 mL each of water and isopropanol. The ink was ultrasonically dispersed in an ice-water bath until uniformly dispersed. The prepared ink was uniformly sprayed onto the microporous layer of the Ballard 3620 gas diffusion layer using an ultrasonic sprayer to form the anode. Using the same method, the platinum-carbon catalyst Hispec 4000 was sprayed onto the microporous layer of another Ballard 3620 gas diffusion layer to serve as the cathode. The platinum loading at the anode was controlled at 0.3 mg / cm³. 2 The cathode platinum loading is controlled at 0.7 mg / cm³.2 , using Fuma high temperature proton exchange membrane AM-40, assembled into a phosphoric acid electrolyte high temperature proton exchange membrane fuel cell and tested.

[0094] The fuel cell was tested under hydrogen-air condition at 160°C with constant current step from 0 to 2.5 A-cm -2 , and the test was repeated until the polarization curves overlapped. The results are shown in Fig. 2. Figure 4 Figure 4 The middle red line is the test result of the catalyst of Example 2.

[0095] Example 3

[0096] 90 mg of ruthenium trichloride and 100 mg of carbon carrier were dissolved and dispersed in 50 mL of triethylene glycol with ultrasonic stirring for 2 h, and then the pH value was adjusted to 11 with sodium hydroxide solution to obtain dispersion liquid A.

[0097] Dispersion liquid A was sealed and then purged with argon, after which carbon monoxide was slowly introduced at a flow rate of 10 mL / min, and it was placed in an oil bath at 120°C for refluxing, and after 2 h of reaction, black ink-like viscous dispersion liquid B was obtained.

[0098] 200 mg of potassium chloroplatinate and 30 mg of phosphomolybdic acid were dissolved and stirred in 100 mL of ethylene glycol to obtain solution C.

[0099] Solution C was added dropwise to dispersion liquid B, and the sample was heated and refluxed at 160°C for 2 h. After the sample was filtered and washed with water, ethanol and acetone by centrifugation, it was dried in a vacuum dryer, and then ground in a mortar. 2 nm cluster-type platinum ruthenium molybdenum nanoparticles supported on a carbon carrier were obtained.

[0100] The obtained catalyst was prepared into ink for fuel cell testing, and the ink composition was as follows: 20 mg of catalyst, 0.5 mL of 5 wt% Nafion solution, and 4 mL of each of water and isopropyl alcohol as solvent; the ink was placed in an ice water bath and ultrasonically dispersed until uniform; the prepared ink was uniformly sprayed on one side of a Gore 15 μm thick proton exchange membrane to form an anode, and a commercial platinum carbon catalyst Hispec 4000 was sprayed on the other side to form a cathode, and the catalyst-sprayed proton exchange membrane was placed in a fuel cell testing fixture for fuel cell testing, with a platinum loading of 0.1 mg / cm 2 on the anode and 0.4 mg / cm 2 on the cathode.

[0101] The fuel cell was tested under hydrogen-air condition at 80°C with constant current step from 0 to 4 A-cm -2 , and the test was repeated until the polarization curves overlapped.

[0102] The fuel cell was controlled at 1 A-cm​-2 The initial potential was obtained after the constant current discharge, and then the anode fuel gas pure hydrogen was switched to hydrogen atmosphere containing 5 ppm NH3, and the whole process was kept at 1 A·cm -2 The ammonia tolerance hydrogen oxidation stability test was carried out by constant current discharge, and the results are shown in the following table. Figure 5 It can be seen that the prepared catalyst can maintain high activity for a long time in the hydrogen atmosphere containing 5 ppm NH3, and the cell voltage does not decay for a long time.

[0103] Example 4

[0104] 50 mg of ruthenium acetate and 100 mg of carbon carrier were dissolved and dispersed in 50 mL of glycerol under ultrasonic stirring for 2 h, and then the pH value was adjusted to 10 by using a sodium hydroxide solution to obtain dispersion liquid A.

[0105] After the dispersion liquid A was sealed and purged with argon, carbon monoxide was slowly introduced at a flow rate of 10 mL / min, and then the system was placed in an oil bath at 120°C for reflux, and after 2 h of reaction, a black ink-like viscous dispersion liquid B was obtained.

[0106] 80 mg of platinum tetrachloride was dissolved by heating and stirring in 100 mL of glycerol to obtain solution C.

[0107] Solution C was added dropwise to dispersion liquid B, and the system was kept at 190°C for 2 h of heating and reflux. After the sample was filtered and washed with water, ethanol and acetone by centrifugation, it was dried in a vacuum dryer, and then ground in a mortar. 1.8 nm cluster-type platinum-ruthenium nanoparticles supported on a carbon carrier were obtained.

[0108] The obtained catalyst was prepared into ink for fuel cell test, and the ink composition was as follows: 20 mg of catalyst, 0.5 mL of 5 wt% Nafion solution, and 4 mL of water and isopropyl alcohol each; the ink was placed in an ice water bath and ultrasonically dispersed until uniform; the prepared ink was uniformly sprayed on one side of a Gore 15 μm thick proton exchange membrane to form an anode, and a commercial platinum-carbon catalyst Hispec 4000 was sprayed on the other side to form a cathode; the proton exchange membrane with catalyst sprayed thereon was placed in a fuel cell test fixture for fuel cell test, and the platinum loading of the anode was 0.1 mg / cm 2 , and the platinum loading of the cathode was 0.4 mg / cm 2 .

[0109] The fuel cell was controlled at 80°C under hydrogen-air conditions, and the polarization curve was obtained by constant current step between 0 and 4 A·cm -2 , and the test was repeated until the curves coincided.

[0110] The fuel cell was controlled at 1 A·cm -2The initial potential was obtained by constant current discharge, and then the anode fuel gas pure hydrogen was switched to hydrogen atmosphere containing 1 ppm H2S, and the whole process maintained 1 A·cm -2 The H2S tolerance hydrogen oxidation stability test was carried out by constant current discharge, and the results are shown in Figure 6 It can be seen that the prepared catalyst can maintain high activity for a long time in hydrogen atmosphere containing 1 ppm H2S, and the cell voltage does not decay for a long time.

[0111] Example 5

[0112] 50 mg of ruthenium acetate and 100 mg of carbon carrier were dissolved and dispersed in 50 mL of glycerol, and ultrasonic stirring was carried out for 2 h. Then, the pH value was adjusted to 10.5 by using sodium hydroxide solution to obtain dispersion liquid A.

[0113] After sealing the dispersion liquid A, argon was blown, then carbon monoxide was slowly introduced at a flow rate of 10 mL / min, and it was placed in an oil bath at 90°C for reflux. After reaction for 3 h, black ink-like viscous dispersion liquid B was obtained.

[0114] 100 mg of sodium hexahydroxyplutonate was dissolved and stirred in 100 mL of ethylene glycol to obtain solution C.

[0115] Solution C was added dropwise to dispersion liquid B, and heating reflux was maintained at 190°C for 2 h. After the sample was filtered and washed with water, ethanol and acetone by centrifugation, it was dried in a vacuum dryer, and then ground in a mortar. 2.2 nm cluster type platinum ruthenium nanoparticles supported on carbon carrier were obtained.

[0116] The obtained catalyst was prepared into ink for fuel cell test. The ink composition was: catalyst 20 mg, 5 wt% Nafion solution 0.5 mL, solvent water and isopropyl alcohol each 4 mL; the ink was placed in an ice water bath and ultrasonically dispersed until uniform; the prepared ink was uniformly sprayed on one side of Gore 15 μm thick proton exchange membrane to form an anode, and a commercial platinum carbon catalyst Hispec 4000 was sprayed on the other side to form a cathode. The proton exchange membrane with catalyst sprayed thereon was placed in a fuel cell test fixture for fuel cell test. The platinum loading of the anode was 0.1 mg / cm 2 , and the platinum loading of the cathode was 0.4 mg / cm 2 .

[0117] The fuel cell was controlled at 80°C under hydrogen-air condition, and the polarization curve was obtained by constant current step between 0 and 3.5 A·cm -2 . The test was repeated until the curves coincided.

[0118] The fuel cell was controlled at 1 A·cm -2The initial potential was obtained after constant current discharge, and then the anode fuel gas was switched from pure hydrogen to hydrogen atmosphere containing 200 ppm CO + 2% O2, and the current was maintained at 1 A-cm -2 The results were similar to those of Example 1. Figure 3 Similarly, the prepared catalyst could maintain high activity for a long time in hydrogen atmosphere containing 200 ppm CO + 2% O2, and the cell voltage did not decay for a long time.

[0119] Example 6

[0120] 50 mg of ruthenium acetylacetonate and 100 mg of carbon support were dissolved and dispersed in 50 mL of glycerol under ultrasonic stirring for 2 h, and then the pH value was adjusted to 11 using a sodium hydroxide solution to obtain dispersion liquid A.

[0121] Dispersion liquid A was sealed and purged with argon, and then carbon monoxide was slowly introduced at a flow rate of 10 mL / min, and the system was placed in an oil bath at 95°C for reflux. After 2.5 h of reaction, black ink-like viscous dispersion liquid B was obtained.

[0122] 80 mg of platinum tetrachloride and 80 mg of cobalt chloride were dissolved and stirred in 100 mL of ethylene glycol to obtain solution C.

[0123] Solution C was added dropwise to dispersion liquid B, and the system was kept at 190°C for 2 h of heating and reflux. After the sample was filtered and washed with water, ethanol, and acetone by centrifugation, it was dried in a vacuum dryer, and then ground in a mortar. 1.75 nm cluster-type platinum-ruthenium-cobalt nanoparticles supported on a carbon support were obtained.

[0124] The obtained catalyst was prepared into ink for fuel cell testing. The ink composition was as follows: 20 mg of catalyst, 0.5 mL of 5 wt% Nafion solution, and 4 mL of each of water and isopropyl alcohol as solvent. The ink was placed in an ice water bath and ultrasonically dispersed until uniform. The prepared ink was uniformly sprayed onto the microporous layer of a gas diffusion layer (Ballard 3620) using an ultrasonic spray machine to form an anode, and platinum-carbon catalyst Hispec 4000 was sprayed onto the microporous layer of another gas diffusion layer (Ballard 3620) as a cathode using the same method. The platinum loading of the anode was controlled at 0.3 mg / cm 2 , and the platinum loading of the cathode was controlled at 0.7 mg / cm 2 A commercial high-temperature proton exchange membrane AM-40 from Fuma was used, and a phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell was assembled and tested.

[0125] The fuel cell was tested under hydrogen-air conditions at 160°C at a current density of 0-2.5 A-cm -2The constant current step between 0-3.5 A-cm -2 obtained the polarization curve, and the test was repeated until the curves overlapped. The test results showed that the high-temperature proton exchange membrane fuel cell with the above catalyst as the anode in phosphoric acid electrolyte had excellent discharge performance and power and excellent resistance to phosphoric acid poisoning.

[0126] Example 7

[0127] 50 mg of ruthenium trichloride and 100 mg of carbon carrier were dissolved and dispersed in 50 mL of glycerol, and ultrasonic stirring was performed for 2 h. A sodium hydroxide solution was used to adjust the pH to 10.8, and dispersion liquid A was obtained.

[0128] Dispersion liquid A was sealed, purged with argon, and then carbon monoxide was slowly introduced at a flow rate of 10 mL / min. The dispersion liquid was placed in an oil bath at 95°C and refluxed for 2.5 h, and black ink-like viscous dispersion liquid B was obtained.

[0129] 100 mg of potassium hexahydroxyplatinate and 20 mg of tin chloride were dissolved and stirred in 100 mL of ethylene glycol to obtain solution C.

[0130] Solution C was added dropwise to dispersion liquid B, and heating reflux was maintained at 180°C for 4 h. After the sample was filtered and washed with water, ethanol, and acetone by centrifugation, it was dried in a vacuum dryer, and then ground in a mortar. 2 nm cluster-type platinum ruthenium tin nanoparticles supported on a carbon carrier were obtained.

[0131] The obtained catalyst was prepared into ink for fuel cell testing. The ink composition was as follows: 20 mg of catalyst, 0.5 mL of 5 wt% Nafion solution, and 4 mL of each of water and isopropyl alcohol as solvent. The ink was placed in an ice water bath and ultrasonically dispersed until uniform. The prepared ink was uniformly sprayed on one side of a Gore 15 μm thick proton exchange membrane as an anode by using an ultrasonic spray machine, and a commercial platinum carbon catalyst Hispec 4000 was sprayed on the other side as a cathode. The proton exchange membrane with the sprayed catalyst was placed in a fuel cell test fixture for fuel cell testing. The platinum loading of the anode was 0.1 mg / cm 2 , and the platinum loading of the cathode was 0.4 mg / cm 2 .

[0132] The fuel cell was controlled to have a constant current discharge of 1 A-cm -2 , and the initial potential was obtained after the curve was stable. Then, the anode fuel gas pure hydrogen was switched to a hydrogen atmosphere containing 200 ppm CO+2% O2, and the current was maintained at 1 A-cm -2 .

[0133] The constant current step between 0-3.5 A-cm -2 obtained the polarization curve, and the test was repeated until the curves overlapped. The test results showed that the high-temperature proton exchange membrane fuel cell with the above catalyst as the anode in phosphoric acid electrolyte had excellent discharge performance and power and excellent resistance to phosphoric acid poisoning. -2The hydrogen oxidation stability test in the presence of carbon monoxide was carried out under constant current discharge. The test results showed that the catalyst could maintain high activity for a long time, and the cell voltage did not decay for a long time.

[0134] Example 8

[0135] 50 mg of ruthenium acetate and 100 mg of carbon carrier were dissolved and dispersed in 50 mL of glycerol under ultrasonic stirring for 2 h, and then the pH value was adjusted to 11.2 using a sodium hydroxide solution to obtain dispersion liquid A.

[0136] After sealing the dispersion liquid A, argon was blown, and then carbon monoxide was slowly introduced at a flow rate of 10 mL / min, and the dispersion liquid was placed in an oil bath at 95°C for reflux. After 2.5 h of reaction, a black ink-like viscous dispersion liquid B was obtained.

[0137] 80 mg of potassium hexahydroxyplatinate was dissolved and stirred in 100 mL of ethylene glycol to obtain solution C.

[0138] Solution C was added dropwise to dispersion liquid B, and the mixture was heated and refluxed at 180°C for 4 h. After the sample was filtered and washed with water, ethanol and acetone by centrifugation, it was dried in a vacuum dryer, and then ground in a mortar. 1.85 nm cluster-type platinum-ruthenium nanoparticles supported on a carbon carrier were obtained.

[0139] The obtained catalyst was prepared into ink for fuel cell test. The ink composition was as follows: 20 mg of catalyst, 0.5 mL of 5 wt% Nafion solution, and 4 mL of water and isopropyl alcohol each. The ink was placed in an ice water bath and ultrasonically dispersed until uniform. The prepared ink was uniformly sprayed onto the microporous layer of a gas diffusion layer Ballard 3620 using an ultrasonic spray machine to form an anode. Platinum-carbon catalyst Hispec 4000 was sprayed onto the microporous layer of another gas diffusion layer Ballard 3620 using the same method to form a cathode. The platinum loading of the anode was controlled to be 0.3 mg / cm 2 , and the platinum loading of the cathode was controlled to be 0.7 mg / cm 2 . A commercial high-temperature proton exchange membrane AM-40 from Fuma was used, and a phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell was assembled and tested.

[0140] The fuel cell was tested under hydrogen-air conditions at 160°C by constant current step between 0 and 2.5 A·cm -2 . The polarization curve was obtained, and the test was repeated until the curves coincided. The test results showed that the phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell with the above-mentioned catalyst as the anode had excellent discharge performance and power, and had excellent resistance to phosphoric acid poisoning.

[0141] The catalysts prepared in Examples 2-8 above were tested according to the method of Example 1. It was found that the platinum in the catalysts was dominated by platinum-oxygen coordination. The platinum-oxygen coordination number was fitted to be 3-5.

[0142] Comparative Example 1

[0143] A commercial PtRu / C catalyst purchased from Johnson Matthey was formulated into ink for fuel cell testing. The ink composition was: catalyst 20 mg, 5 wt% Nafion solution 0.5 mL, solvent water and isopropanol 4 mL each. The ink was placed in an ice water bath and sonicated until uniformly dispersed. The ink was uniformly sprayed onto one side of a proton exchange membrane using an ultrasonic spray machine as an anode. A commercial platinum carbon catalyst Hispec 4000 was sprayed onto the other side of the proton exchange membrane as a cathode. The proton exchange membrane with catalysts sprayed thereon was placed in a fuel cell testing fixture for fuel cell testing. The platinum loading of the anode was 0.1 mg / cm 2 , and the platinum loading of the cathode was 0.4 mg / cm 2 .

[0144] The fuel cell was subjected to a constant current step between 0-3.5 A·cm -2 at 80°C under hydrogen-air conditions to obtain a polarization curve. The test was repeated until the curves overlapped.

[0145] The fuel cell was controlled to discharge at a constant current of 1 A·cm -2 . After the curve was stable, the initial potential was obtained. Then, pure hydrogen was switched to a hydrogen atmosphere containing 200 ppm CO + 2% O2, and the constant current discharge was maintained at 1 A·cm -2 for the entire process to test the carbon monoxide tolerance of the hydrogen oxidation stability. The test results are shown in Figure 3 (blue line), which shows that the voltage of the fuel cell decreased by 260 mV in a short time.

[0146] Comparative Example 2

[0147] A commercial platinum carbon catalyst Hispec 4000 was formulated into ink for fuel cell testing. The ink composition was: catalyst 20 mg, 5 wt% Nafion solution 0.5 mL, solvent water and isopropanol 4 mL each. The ink was placed in an ice water bath and sonicated until uniformly dispersed. The ink was uniformly sprayed onto the microporous layer of a gas diffusion layer Ballard 3620 to form an anode using an ultrasonic spray machine. A platinum carbon catalyst Hispec 4000 was sprayed onto the microporous layer of another gas diffusion layer Ballard 3620 as a cathode using the same method. The platinum loading of the anode was controlled to be 0.7 mg / cm 2 , and the platinum loading of the cathode was controlled to be 0.7 mg / cm 2The Fuma commercial high temperature proton exchange membrane AM-40 was used to assemble the phosphoric acid electrolyte high temperature proton exchange membrane fuel cell for testing.

[0148] The fuel cell was tested under hydrogen-air condition at 160℃ with constant current step from 0 to 2.5 A·cm -2 between 0 and 2.5 A·cm Figure 4 Figure 4 The middle gray line is the test result of the catalyst of Comparative Example 2. It can be seen that the phosphoric acid electrolyte high temperature proton exchange membrane fuel cell prepared by using the catalyst of Example 2 as the anode has better discharge performance and power than the phosphoric acid electrolyte high temperature proton exchange membrane fuel cell prepared by using the commercial platinum-carbon catalyst as the anode, due to the excellent phosphoric acid poisoning resistance of the catalyst.

[0149] The above describes the present application in combination with preferred embodiments, but these embodiments are only exemplary and are used for illustration only. On this basis, various substitutions and improvements can be made to the present application, and these all fall within the protection scope of the present application.​

Claims

1. A fuel cell having an anode comprising a fuel cell anode catalyst resistant to poisoning, wherein, The fuel cell anode catalyst comprises a support and alloy nanoparticle clusters supported on the support; the alloy nanoparticle clusters comprise ruthenium, platinum and optionally a third metal; the third metal is one or more selected from palladium, molybdenum, cobalt, tin, tungsten; the alloy nanoparticle clusters have a particle size of 1-2.5 nm, wherein at least part of the platinum atoms are coordinated with oxygen and the platinum oxygen coordination number is greater than 2, and wherein the fuel cell is a phosphoric acid electrolyte high-temperature proton exchange membrane fuel cell.

2. The fuel cell according to claim 1, wherein the platinum oxygen coordination number is 3-5.

3. The fuel cell according to claim 1 or 2, wherein The loading of ruthenium in the fuel cell anode catalyst is 1%-30%; and / or The loading of platinum in the fuel cell anode catalyst is 1%-60%; and / or The loading of the third metal in the fuel cell anode catalyst is 1%-30%.

4. A method of making a fuel cell anode catalyst as defined in any one of claims 1 to 3, wherein, Comprising the following steps: (1) providing a basic dispersion liquid A comprising a first polyol and a support and dissolving a ruthenium precursor therein; (2) introducing carbon monoxide into the dispersion liquid A in step (1) and performing first heating reflux to obtain a dispersion liquid B; (3) dissolving a platinum precursor and optionally a third metal precursor in a second polyol to obtain a solution C; (4) dropping the solution C from step (3) into the dispersion liquid B from step (2) and performing second heating reflux, and then performing solid-liquid separation to obtain the fuel cell anode catalyst.

5. The method of claim 4, wherein, In step (1), the ruthenium precursor is one or more selected from ruthenium acetate, ruthenium trichloride trihydrate, ruthenium trichloride, ruthenium acetylacetonate; and / or The support is one or more selected from carbon support, inorganic oxide support, inorganic nitride support, inorganic carbide support; the carbon support is one or more selected from porous carbon, mesoporous carbon; and / or The mass ratio of the ruthenium precursor to the first polyol is (0.0001-0.1):1, and the mass ratio of the support to the first polyol is (0.0001-0.1):

1.

6. The method of claim 4, wherein, The pH value of the dispersion liquid A in step (1) is 8-11.

5.

7. The method of claim 4, wherein, The flow rate of the carbon monoxide introduced in step (2) is 0.1-500 mL / min; and / or The first heating reflux is performed at 80-120℃ for 2-4 h; and / or Step (2) further comprises the following steps before introducing carbon monoxide: The dispersion liquid A is sealed and purged with inert gas.

8. The method of claim 7, wherein, The flow rate of the carbon monoxide introduced in step (2) is 5-10 mL / min.

9. The method of claim 4, wherein, The platinum precursor in step (3) is one or more selected from chloroplatinic acid hexahydrate, platinum tetrachloride, potassium chloroplatinate, sodium hexahydroxyplatinate, potassium hexahydroxyplatinate; The third metal precursor comprises one or more of chloride salt, nitrate salt, sulfate salt of the third metal; and / or The first polyol and the second polyol are each independently selected from C2-C8 diols and / or triols; and / or The mass ratio of the total mass of the platinum precursor and the third metal precursor to the second polyol is (0.0001-0.1):

1.

10. The method of claim 9, wherein, The third metal precursor is selected from one or more of palladium chloride, phosphomolybdic acid, cobalt chloride, and tin chloride.

11. The method of claim 9, wherein, The first polyol and the second polyol are each independently selected from one or more of ethylene glycol, propylene glycol, glycerol, and triethylene glycol.

12. The method of claim 4, wherein, The second heating reflux in step (4) is performed at 150-200 °C for 2-5 h.

13. The method of claim 4, wherein, Step (4) further comprises washing, vacuum drying, and grinding after the solid-liquid separation.

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