Fuel cell catalysts with noble metal as catalytically active component and methods of making and using same

Abstract

The application discloses a fuel cell catalyst with noble metal as a catalytically active component and a preparation method and application thereof, and the preparation method comprises the following steps: (1) dissolving a noble metal precursor in water to form a noble metal precursor solution; (2) mixing and adsorbing the noble metal precursor solution and a carrier precursor, and then centrifuging and drying; and (3) high-temperature heat treating the dried product obtained in the step (2) at 700-900 DEG C for 1-5 hours under a reducing atmosphere to obtain the catalyst. The catalyst prepared by the application has good dispersity and uniform distribution, no additional carbon carrier needs to be added in the preparation process, the preparation process is simple, and the catalyst can be suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of fuel cell catalyst technology, specifically to a fuel cell catalyst with a noble metal as the catalytically active component, its preparation method, and its application. Background Technology

[0002] A fuel cell is a device that can efficiently and cleanly convert the chemical energy of fuel into electrical energy. Fuel cell catalysts include Pt / C catalysts, Pt alloy catalysts, non-precious metal catalysts, and non-metallic catalysts. Currently, the activity and stability of non-Pt catalysts are inferior to those of Pt-based catalysts. Furthermore, the presence of transition metals M (M = Fe, Co, Ni, Cr, and Mn, etc.) in Pt alloys can alter the geometric, electronic, and stress effects of Pt, thereby improving the activity and stability of Pt catalysts while reducing the amount of Pt required. However, the synthesis of existing Pt alloy catalysts often faces the following technical bottlenecks:

[0003] (1) The need for advanced functionalized carbon support mass production technology: Newly purchased carbon supports contain a large amount of organic matter and exhibit chemical inertness, lacking sufficient active sites to anchor metal salt precursors and catalyst particles. To address this issue, strong acid and oxidant treatment is typically required to introduce polar oxygen groups onto the carbon support surface, thereby enhancing the precursor adsorption capacity. However, on the one hand, these introduced polar groups are the origin of support corrosion and damage, leading to corrosion of the entire graphitized carbon support and reduced catalyst stability. On the other hand, the strong acid and oxidant treatment process not only requires equipment resistant to strong acid corrosion and oxidation, but also necessitates extensive deionized water cleaning of the support, and specialized treatment facilities are required for waste acid and wastewater.

[0004] (2) The deposition method used in the preparation process suffers from problems such as poor dispersion and low loading of metal precursors. To obtain catalyst particles with high loading, uniform dispersion, and controllable particle size and catalyst composition, it is first necessary to adsorb the metal salt precursors onto the carbon support surface with high uniform dispersion and high loading. However, since the adsorption of metal precursors on the support surface is mainly physical adsorption, its adsorption capacity is limited. To increase adsorption, precipitation or colloidal methods are usually used to load the metal precursors onto the support surface. However, since the particle size of the carbon support is very small (about 30 nanometers), in order to reduce the problem of uneven distribution of precursors on the carbon support surface caused by carbon support aggregation, it is usually necessary to first disperse the support in a large amount of solvent before adsorption. This method not only requires the design of a special reactor to ensure uniform dispersion of the support, but also makes the subsequent washing, separation, and drying processes more complicated, thus greatly increasing the cost of the catalyst.

[0005] (3) The particle size and component content of the final product need to be controlled under high temperature conditions. High-temperature reduction heat treatment (>700℃) is an essential condition for converting metal salt precursors into intermetallic compound catalysts. However, due to the weak anchoring effect of traditional carbon supports on the adsorbed and precipitated metal salt precursors on their surface, the reduced metal nanoparticles are prone to sintering and agglomeration during high-temperature reduction heat treatment, thereby reducing the active surface area and catalytic activity of the catalyst. In addition, during the heat treatment process, due to the influence of the reducing atmosphere, alloy nanoparticles that have formed a good intermetallic compound structure are prone to component segregation, further reducing the catalyst activity.

[0006] Due to the aforementioned technical challenges, traditional methods typically require the development of specialized equipment and production lines, as well as the establishment of stringent quality control standards. Therefore, developing a simple process capable of mass-producing fuel cell catalysts is of great significance. Summary of the Invention

[0007] To address the aforementioned shortcomings of existing technologies, the present invention aims to provide a fuel cell catalyst with precious metals as the catalytic active component, its preparation method, and its application. This addresses the problems of uneven particle size and elemental distribution in existing fuel cell catalysts, the need for additional carbon supports during preparation, and the difficulty in controlling particle size and elemental distribution due to high catalyst synthesis temperatures, thus hindering industrial production.

[0008] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A method for preparing a fuel cell catalyst with noble metal as the catalytically active component is provided, comprising the following steps:

[0009] (1) Dissolve the noble metal precursor in water to form a noble metal precursor solution;

[0010] (2) The noble metal precursor solution and the carrier precursor are mixed and adsorbed, then centrifuged and dried;

[0011] (3) The product obtained from drying in step (2) is heat-treated at 700-900℃ for 1-5 hours under a reducing atmosphere to obtain the product.

[0012] The beneficial effects of the above technical solution are as follows: This application does not require the addition of an additional carbon support. It only requires mixing the noble metal precursor solution and the support precursor. The carbon support precursor adsorbs the noble metal onto its surface and / or interior. After centrifugation and drying, a support precursor loaded with noble metal is formed. This adsorption process allows for control of the adsorption amount, thereby controlling the loading of the active component in the catalyst. Simultaneously, the noble metal can be uniformly distributed on the support precursor. The carbon support precursor loaded with noble metal is then subjected to high-temperature heat treatment at 700-900℃ under a reducing atmosphere. This heat treatment process under a reducing atmosphere reduces the metal precursor to an alloy, while simultaneously forming a nitrogen-doped porous carbon support, thus forming a catalyst with noble metal as the main active component and nitrogen-doped porous carbon as the support. No additional carbon support is required during the entire preparation process. During the high-temperature heat treatment, while the noble metal forms noble metal nanoparticles, the support precursor also forms a nitrogen-doped porous carbon support. The formed noble metal nanoparticles are loaded onto the carbon support and can form cluster structures. Traditional catalysts tend to agglomerate during the MEA preparation process, resulting in some nanoparticles being buried and unable to participate in fuel cell reactions. However, the catalyst obtained by this invention has a cluster structure with larger particles, which prevents re-agglomeration and avoids the shortcomings of traditional catalysts.

[0013] Furthermore, the precious metal is at least one of gold (Au), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).

[0014] The beneficial effects of the above technical solution are as follows: the catalyst of the present invention uses precious metals as catalytic active ingredients. Precious metals can be the only catalytic active ingredient, or the main catalytic active ingredient, supplemented by co-catalytic active ingredients, or precious metals can be one of the main catalytic active ingredients, supplemented by other main catalytic active ingredients and co-catalytic active ingredients.

[0015] Furthermore, in step (1), in addition to precious metals, other metals are also included, such as at least one of cobalt (Co), iron (Fe), nickel (Ni), tin (Sn), and molybdenum (Mo). When the precious metal precursor is dissolved in water, the precious metal and the above-mentioned metals can be dissolved in water at a molar ratio of 1-5:1, according to the needs of the target product, so that the concentration of the precious metal reaches 110-130 mmol / L. Ultrapure water can be selected. Metals are added in the form of acids or salts. For example, gold is added in the form of chloroauric acid, ruthenium in the form of ammonium hexachlororuthenate, potassium pentachlororuthenate, and potassium hexacyanorubate, rhodium in the form of sodium rhodium chlorochloroacetate, palladium in the form of potassium chloropalladium, sodium chloropalladium, and ammonium chloropalladium, osmium in the form of sodium hexachloroosmium acetate, iridium in the form of ammonium hexachloroiridium, platinum in the form of chloroplatinic acid, potassium chloroplatinate, and potassium chloroplatinate, cobalt in the form of sodium cobalt cyanide and potassium cobalt cyanide, iron in the form of sodium ferrocyanide, potassium ferrocyanide, and potassium ferrocyanide, nickel in the form of potassium nickel cyanide and potassium hexacyanide nickelate, tin in the form of sodium stannate, potassium stannate, and zinc stannate, and molybdenum in the form of ammonium molybdate, sodium molybdate, potassium molybdate, and zinc molybdate.

[0016] Furthermore, the carrier precursor is a resin or a non-resin; the resin is preferably an anionic resin.

[0017] The beneficial effects of the above-mentioned further technical solutions are as follows: The carrier precursor is a substance that can form a porous carbon structure through high-temperature heat treatment. When the carrier precursor is a resin, the resin is usually an anionic resin. The pore structure and size of the resin can be changed in different solvents. In a suitable liquid solvent, the resin skeleton structure will exhibit a pseudo-solution state (swelling state) due to swelling, thereby producing a microporous structure. Alternatively, the resin skeleton may be a permanent macropore, while the swelling state is characterized by a certain degree of swelling pores only appearing on the surface of the inner wall of the macropores. When noble metals and carrier precursors (resins) are mixed, the resin is first added to water, and then a noble metal solution or a noble metal solution and other metal solutions are added. Alternatively, the noble metal solution or a noble metal solution and other metal solutions are mixed with the resin or pretreated resin. Through the adsorption of the resin, the noble metal or noble metals and other metals can be adsorbed into the pores of the resin, thereby loading the noble metal. During the adsorption process, heating can be used to promote the adsorption rate and improve the loading efficiency. The heating temperature can be 40-70℃, preferably 50℃.

[0018] Furthermore, the resin is a macroporous anion exchange resin with tertiary amine groups [-N(CH3)2]. This resin is rich in nitrogen and carbon sources and can form porous nitrogen-doped carbon materials under high-temperature pyrolysis conditions, effectively supporting noble metals. This resin can be used directly or pretreated, such as by grinding and pulverizing, with a grinding mesh of 30-60 mesh, preferably 60 mesh. The portion larger than 60 mesh is the pretreated anion exchange resin. Specific resin types used in this invention include MP62, D301, D301FC, D316, and D900.

[0019] Furthermore, in step (3), the reducing atmosphere is a mixture of hydrogen and argon or hydrogen and nitrogen, with a hydrogen volume content of 5-40%, preferably 20%.

[0020] Furthermore, in step (3), the high-temperature heat treatment temperature is 700-900℃ and the time is 1-3h, preferably the heat treatment temperature is 800℃ and the treatment time is 2h.

[0021] The beneficial effects of the above-mentioned further technical solution are as follows: under the heat treatment temperature and time conditions, the support precursor can form a porous carbon support structure without the need to add an extra carbon support. At the same time, during the high-temperature heat treatment process, noble metals and other materials can be well loaded on the support, and the loading amount is controllable, resulting in a catalyst with a large electrochemical area and excellent catalytic activity.

[0022] Furthermore, the method also includes: acid washing of the product obtained in step (3), wherein the acid washing solution is a 0.5-2M nitric acid or sulfuric acid solution, the acid washing temperature is 60-80℃, and the acid washing time is 2-10h. Preferably, the nitric acid concentration is 1M, the acid washing temperature is 60℃, and the acid washing time is 2h; the sulfuric acid concentration is 0.5M, the acid washing temperature is 60℃, and the acid washing time is 2h.

[0023] The beneficial effects of the above-mentioned further technical solutions are as follows: the acid washing process is to remove impurities on the catalyst surface and remove excess non-precious metals, so that precious metals such as Pt expose more active sites.

[0024] The fuel cell catalysts prepared by the above-described method, which use noble metals as catalytic active components, include PtCo / C, PtFe / C, PtNi / C, PtPd / C, PtCoAu / C, PtPdAu / C, PtRu / C, PtRuCo / C, PtSnCo / C, Pt-MoC / C, PtRu-MoC / C, PtMo / C, PtRuNi / C, PtRuMoNi / C, and PtRuMo / C catalysts.

[0025] The active components in the aforementioned catalysts can synthesize intermetallic compounds or substances that are not intermetallic compounds. The active components in the catalyst can be noble metals or substances formed by combining noble metals with other metals. When forming the catalyst, noble metals can be supported on a porous carbon support, or noble metals combined with other metals can be supported on a porous carbon support as active components. Alternatively, noble metals combined with other metals can be supported on a support to form an integral active component, which is then supported on a porous carbon support. Examples include Pt-MoC / C and PtRu-MoC / C. In these two catalysts, MoC exists as a support; that is, Pt or PtRu is first supported on MoC to form an integral component, and then this integral component is supported on a porous carbon support to form the final catalyst.

[0026] The catalyst prepared by the above method comprises a nitrogen-doped porous carbon support and a catalytically active component attached to the porous carbon support. The catalytically active component comprises noble metal nanoparticles with a particle size of 2-5 nm, a carbon support size of 30-1000 nm, and the noble metal accounting for 10-60% of the total mass of the catalyst. The noble metal nanoparticles in the catalyst of this invention can be uniformly dispersed on the porous carbon support, exhibiting good dispersibility.

[0027] The above-mentioned fuel cell catalysts with precious metals as catalytic active components are used in the preparation of fuel cells.

[0028] The aforementioned fuel cell catalysts with precious metals as catalytically active components can be used as cathode oxygen reduction catalysts in fuel cells, and also as anode catalysts for hydrogen hydroxide and direct methanol fuel cells. Examples of catalysts used as cathode oxygen reduction catalysts include PtCo / C, PtFe / C, PtNi / C, PtPd / C, PtCoAu / C, and PtPdAu / C; examples of catalysts used as anode catalysts for hydrogen hydroxide and direct methanol fuel cells include PtRu / C, PtRuCo / C, PtSnCo / C, Pt-MoC / C, and PtRu-MoC / C.

[0029] A fuel cell includes the aforementioned fuel cell catalyst in which a precious metal is the catalytically active component.

[0030] The beneficial effects of this invention are as follows:

[0031] The catalyst provided by this invention comprises a porous carbon support and a catalytically active component attached to the porous carbon support. The catalytically active component includes noble metal nanoparticles. The active component in the catalyst can synthesize intermetallic compounds or substances that are not intermetallic compounds. The active component in the catalyst can be a noble metal or a substance formed by combining a noble metal with other metals. When forming the catalyst, the noble metal can be loaded onto the porous carbon support, or a noble metal combined with other metals can be loaded onto the porous carbon support as an active component, or a noble metal combined with other metals can be loaded onto the support to form an active component, which is then loaded onto the porous carbon support. The catalyst prepared by this invention has good dispersibility and uniform distribution. No additional carbon support needs to be added during the preparation process, making the preparation process simple and suitable for industrial production. Attached Figure Description

[0032] Figure 1 The images show TEM images and mapping diagrams of the PtCo / C catalyst.

[0033] Figure 2 The images show the XRD pattern, LSV curve, CO dissolution curve, single-cell polarization curve, and power density curve of the PtCo / C catalyst.

[0034] Figure 3 This is a TEM image of the PtFe / C catalyst.

[0035] Figure 4 The image shows the XRD pattern and LSV curve of the PtFe / C catalyst.

[0036] Figure 5 This is a TEM image of the PtNi / C catalyst.

[0037] Figure 6 The images show the XRD pattern, LSV curve, and CO dissolution curve of the PtNi / C catalyst.

[0038] Figure 7 This is a TEM image of the PtSnCo / C catalyst.

[0039] Figure 8 The images show the XRD pattern, LSV curve, and CO dissolution curve of the PtSnCo / C catalyst.

[0040] Figure 9 This is a TEM image of the PtCoAu / C catalyst.

[0041] Figure 10 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtCoAu / C catalyst.

[0042] Figure 11 This is a TEM image of the PtPdAu / C catalyst.

[0043] Figure 12 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtPdAu / C catalyst.

[0044] Figure 13 This is a TEM image of the PtPd / C catalyst.

[0045] Figure 14 The images show the XRD pattern, LSV curve, and CO dissolution curve of the PtPd / C catalyst.

[0046] Figure 15 This is a TEM image of the PtRuMo / C catalyst.

[0047] Figure 16 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtRuMo / C catalyst.

[0048] Figure 17 This is a TEM image of the PtRuCo / C catalyst.

[0049] Figure 18 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtRuCo / C catalyst.

[0050] Figure 19 This is a TEM image of the PtRuMoNi / C catalyst.

[0051] Figure 20 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtRuMoNi / C catalyst.

[0052] Figure 21 This is a TEM image of the PtRuNi / C catalyst.

[0053] Figure 22 The images show the XRD pattern, LSV curve, and CO dissolution curve of the PtRuNi / C catalyst.

[0054] Figure 23 This is a TEM image of the PtRu / C catalyst.

[0055] Figure 24 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtRu / C catalyst.

[0056] Figure 25 This is a TEM image of the PtMo / C catalyst.

[0057] Figure 26 The images show the XRD pattern, LSV curve, and CO dissolution curve of the PtMo / C catalyst. Detailed Implementation

[0058] The examples given below are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified, conditions in the examples are performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0059] Example 1: PtCo / C catalyst

[0060] A catalyst, PtCo / C, is prepared by adsorbing H2PtCl6 and K3[Co(CN)6] onto an anion exchange resin. The specific preparation process includes the following steps:

[0061] (1) Take resin MP62, grind it, and pass it through a 60-mesh sieve;

[0062] (2) Take 1g of ground resin MP62 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 5.6mL of H2PtCl6 and 0.1821g of K3[Co(CN)6] to the solution in sequence, stir and mix evenly, adsorb at 50℃ for 6h and then centrifuge and dry.

[0063] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0064] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0065] Example 2: PtCo / C catalyst

[0066] The difference between Example 2 and Example 1 is that the heat treatment temperature in step (3) is 900℃ and the heat treatment time is 1h.

[0067] Example 3: PtCo / C catalyst

[0068] The difference between Example 3 and Example 1 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0069] The PtCo / C catalyst prepared above, taking Example 1 as an example, has its TEM image and mapping diagram shown below. Figure 1 XRD patterns, LSV curves, CO dissolution curves, single-cell polarization curves, and power density curves are shown in [reference needed]. Figure 2 .

[0070] The above tests were conducted using a Gamry electrochemical workstation with a three-electrode system. A glassy carbon electrode loaded with a catalyst was used as the working electrode, a saturated Ag / AgCl electrode was used as the reference electrode, a carbon rod was used as the counter electrode, and a 0.1M HClO4 solution saturated with N2 or O2 was used as the electrolyte.

[0071] LSV: 0.1M O2 saturated HClO4 solution at 10mVs -1 The LSV curve was recorded at the scan rate.

[0072] CO: 0.1M N2 saturated HClO4 solution at 10mVs -1 The scan rate is used to record CO removal.

[0073] Single cell: Polarization curves and power density curves of a single cell assembled with PtCo / C as the cathode and JM-Pt / C as the anode under oxygen test conditions.

[0074] The XRD pattern shows that the PtCo alloy was successfully synthesized, completely consistent with the standard Pt3Co (PDF#00-029-0499). Strong diffraction peaks indicate that Co successfully entered the Pt lattice and has a high degree of alloying. The narrow half-width at half-maximum (WHM) indicates a large particle size, consistent with TEM data. The LSV curve shows that the half-wave potential of PtCo is 0.897 V, comparable to commercial Pt / C (0.895 V). The ECSA (extraction coefficient of carbon) can be calculated to be approximately 58 m from the CO dissolution curve. 2 g -1 The PtCo / C catalyst is slightly larger than that of Pt / C, indicating a greater number of active sites. TEM images show that the catalyst particles are uniformly dispersed on the carbon support, and the mapping diagram shows that Pt and Co are uniformly dispersed, with Pt being more abundant than Co. Furthermore, the polarization and power density curves of the fuel cell show that PtCo / C outperforms JM-Pt / C.

[0075] Example 4: PtFe / C catalyst

[0076] A catalyst PtFe / C is prepared by adsorbing H2PtCl6 and K3[Fe(CN)6] onto an anion exchange resin. The specific preparation process includes the following steps:

[0077] (1) Take resin MP62, grind it, and pass it through a 60-mesh sieve;

[0078] (2) Take 1g of ground resin MP62 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 5.6mL of H2PtCl6 and 0.18g of K3[Fe(CN)6] to the solution in sequence, stir and mix evenly, adsorb at 50℃ for 6h and then centrifuge and dry.

[0079] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0080] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0081] Example 5: PtFe / C catalyst

[0082] The difference between Example 5 and Example 4 is that the heat treatment temperature in step (3) is 900℃ and the heat treatment time is 1h.

[0083] Example 6: PtFe / C catalyst

[0084] The difference between Example 6 and Example 4 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0085] The TEM image of the PtFe / C catalyst prepared above, taking Example 4 as an example, is shown below. Figure 3 XRD patterns and LSV curves are shown in [link to XRD pattern]. Figure 4 (The specific testing process is the same as in Example 1, and so on).

[0086] The XRD pattern shows that the PtFe / C alloy was successfully synthesized. The main peak shifts to a higher angle, indicating alloy formation. The strong diffraction peaks indicate a high degree of alloying. The LSV curve shows that the half-wave potential of PtFe / C is 0.90 V, which is 5 mV higher than that of commercial Pt / C (0.895 V). TEM results show that the PtFe element is uniformly distributed.

[0087] Example 7: PtNi / C catalyst

[0088] A catalyst, PtNi / C, is prepared by adsorbing H2PtCl6 and K3[Ni(CN)6] onto an anion exchange resin. The specific preparation process includes the following steps:

[0089] (1) Take resin MP62, grind it, and pass it through a 60-mesh sieve;

[0090] (2) Take 1g of ground resin MP62 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 5.6mL of H2PtCl6 and 0.18g of K3[Ni(CN)6] to the solution in sequence, stir and mix evenly, adsorb at 50℃ for 6h and then centrifuge and dry.

[0091] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0092] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0093] Example 8: PtNi / C catalyst

[0094] The difference between Example 8 and Example 7 is that the heat treatment temperature in step (3) is 900℃ and the heat treatment time is 1h.

[0095] Example 9: PtNi / C catalyst

[0096] The difference between Example 9 and Example 7 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0097] The TEM image of the PtNi / C catalyst prepared above, taking Example 7 as an example, is shown below. Figure 5 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 6 .

[0098] The XRD pattern confirms the successful synthesis of the PtNi / C alloy. The LSV curve shows a half-wave potential of 0.86 V for PtNi / C, indicating that the particles may have grown larger during reduction, leading to fewer active sites and decreased activity. The ECSA calculated from CO dissolution is 57.41 m. 2 / g, consistent with XRD and LSV results. TEM images show that PtNi is uniformly dispersed on the support, with a uniform elemental distribution.

[0099] Example 10: PtSnCo / C catalyst

[0100] A catalyst, PtSnCo / C, is prepared by adsorbing H2PtCl6, K3[Co(CN)6], and K2SnO3 onto an anion exchange resin. The specific preparation process includes the following steps:

[0101] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0102] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 4.37mL H2PtCl6, 0.141g K3[Co(CN)6] and 0.127g K2SnO3 to the solution in sequence, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0103] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0104] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0105] Example 11: PtSnCo / C catalyst

[0106] The difference between Example 11 and Example 10 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0107] Example 12: PtSnCo / C catalyst

[0108] The difference between Example 12 and Example 10 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0109] The TEM image of the PtSnCo / C catalyst prepared above, taking Example 10 as an example, is shown below. Figure 7 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 8 .

[0110] TEM images show that PtSnCo is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtSnCo / C. LSV curves show that the half-wave potential of PtSnCo / C is 0.88 V. ECSA calculated from CO dissolution is 23.73 m. 2 / g.

[0111] Example 13: PtCoAu / C catalyst

[0112] A catalyst, PtCoAu / C, is prepared by adsorbing H2PtCl6, K3[Co(CN)6], and KAuCl6 onto an anion exchange resin. The specific preparation process includes the following steps:

[0113] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0114] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 4.92mL of H2PtCl6, 0.159g of K3[Co(CN)6] and 0.181g of K2SnO3 to the solution in sequence, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0115] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0116] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0117] Example 14: PtCoAu / C catalyst

[0118] The difference between Example 14 and Example 13 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0119] Example 15: PtCoAu / C catalyst

[0120] The difference between Example 15 and Example 13 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0121] The TEM image of the PtCoAu / C catalyst prepared above, taking Example 13 as an example, is shown below. Figure 9 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 10 .

[0122] The XRD pattern confirms the successful synthesis of the PtCoAu / C alloy. The LSV curve shows a half-wave potential of 0.883 V for PtCoAu / C. The ECSA calculated through CO dissolution is 20.15 m. 2 / g. TEM images show that the catalytically active components are uniformly dispersed on the support, with a uniform elemental distribution.

[0123] Example 16: PtPdAu / C catalyst

[0124] A catalyst, PtPdAu / C, is prepared by adsorbing H2PtCl6, K2PdCl6, and KAuCl6 onto an anion exchange resin. The specific preparation process includes the following steps:

[0125] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0126] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 5.62mL of H2PtCl6, 0.218g of K2PdCl6 and 0.207g of KAuCl6 to the solution in sequence, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0127] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0128] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0129] Example 17: PtPdAu / C catalyst

[0130] The difference between Example 17 and Example 16 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0131] Example 18: PtPdAu / C catalyst

[0132] The difference between Example 18 and Example 16 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0133] The TEM image of the PtPdAu / C catalyst prepared above, taking Example 16 as an example, is shown below. Figure 11 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 12 .

[0134] TEM images show that PtPdAu is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtPdAu / C. LSV curves show that the half-wave potential of PtPdAu / C is 0.888 V. The ECSA calculated by CO dissolution is 46.02 m. 2 / g.

[0135] Example 19: PtPd / C catalyst

[0136] A catalyst PtPd / C is prepared by adsorbing H2PtCl6 and K2PdCl6 onto an anion exchange resin. The specific preparation process includes the following steps:

[0137] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0138] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 6.57mL of H2PtCl6 and 0.254g of K2PdCl6 to the solution in sequence, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0139] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0140] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0141] Example 20: PtPd / C catalyst

[0142] The difference between Example 20 and Example 19 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0143] Example 21: PtPd / C catalyst

[0144] The difference between Example 21 and Example 19 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0145] The TEM image of the PtPd / C catalyst prepared above, taking Example 19 as an example, is shown below. Figure 13 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 14 .

[0146] TEM images show that PtPd is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtPd / C. LSV curves show that the half-wave potential of PtPd / C is 0.858 V. ECSA calculated by CO dissolution is 33.96 m. 2 / g.

[0147] Example 22: PtRuMo / C catalyst

[0148] A catalyst, PtRuMo / C, is prepared by adsorbing H₂PtCl₆, K₂RuCl₅·H₂O, and (NH₄)Mo₇O using an anion exchange resin. 24 The preparation of PtRuMo / C using 4H2O involves the following steps:

[0149] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0150] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then, add 8.44mL of H2PtCl6, 0.2053g of K2RuCl5·H2O and 0.6773g of (NH4)Mo7O to the solution in sequence. 24 ·4H2O, stir to mix evenly, adsorb at 40℃ for 6 hours, then centrifuge and dry;

[0151] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0152] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0153] Example 23: PtRuMo / C catalyst

[0154] The difference between Example 23 and Example 22 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0155] Example 24: PtRuMo / C catalyst

[0156] The difference between Example 24 and Example 22 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0157] The TEM image of the PtRuMo / C catalyst prepared above, taking Example 22 as an example, is shown below. Figure 15 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 16 .

[0158] TEM images show that PtRuMo is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtRuMo / C. LSV curves show that the hydroxylation (HOR) current density of PtRuMo / C is higher than 2.5 mA / cm².-2 The CO desorption peak apex position is lower than that of commercial PtRu (0.5V). The ECSA calculated by CO dissolution is 39.06m. 2 The PtRuMo / C catalyst exhibits a lower methanol oxidation onset potential than the commercial JM PtRu catalyst, which is more conducive to methanol oxidation.

[0159] Example 25: PtRuCo / C catalyst

[0160] A catalyst, PtRuCo / C, is prepared by adsorbing H2PtCl6, K2RuCl5·H2O, and K3[Co(CN)3] onto an anion exchange resin. The specific preparation process includes the following steps:

[0161] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0162] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 5.37mL H2PtCl6, 0.1306g K2RuCl5·H2O and 0.1159g K3[Co(CN)3] to the solution in sequence, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0163] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0164] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0165] Example 26: PtRuCo / C catalyst

[0166] The difference between Example 26 and Example 25 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0167] Example 27: PtRuCo / C catalyst

[0168] The difference between Example 27 and Example 25 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0169] The TEM image of the PtRuCo / C catalyst prepared above, taking Example 25 as an example, is shown below. Figure 17XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 18 .

[0170] TEM images show that PtRuCo is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtRuCo / C. LSV curves show that the HOR current density of PtRuCo / C is less than 2.5 mA / cm². -2 ECSA calculated based on CO leaching is 31.94 m. 2 / g. The CO desorption peak position at 0.5V is similar to that of commercial PtRu (0.5V), indicating that the methanol oxidation onset potential of the PtRuCo / C catalyst is lower than that of commercial PtRu.

[0171] Example 28: PtRuMoNi / C catalyst

[0172] A catalyst, PtRuMoNi / C, is prepared by adsorbing H2PtCl6, K2RuCl5·H2O, and (NH4)Mo7O using an anion exchange resin. 24 The preparation of PtRuMoNi / C with K2Ni(CN)4 includes the following steps:

[0173] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0174] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then, add 4.22mL of H2PtCl6, 0.1026g of K2RuCl5·H2O and 0.3387g of (NH4)Mo7O to the solution in sequence. 24 Mix 0.071g K2Ni(CN)4 with water, stir until homogeneous, adsorb at 40℃ for 6h, and then centrifuge and dry.

[0175] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0176] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0177] Example 29: PtRuMoNi / C catalyst

[0178] The difference between Example 29 and Example 28 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0179] Example 30: PtRuMoNi / C catalyst

[0180] The difference between Example 30 and Example 28 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0181] The TEM image of the PtRuMoNi / C catalyst prepared above, taking Example 28 as an example, is shown below. Figure 19 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 20 .

[0182] TEM images show that PtRuMoNi is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtRuMoNi / C. LSV curves show that the HOR current density of PtRuMoNi / C is greater than 2.5 mA / cm². -2 ECSA calculated based on CO leaching is 33.52m. 2 / g, the CO desorption peak position is higher than that of the commercial PtRu catalyst (0.5V), and the methanol oxidation onset potential of the PtRuMoNi / C catalyst is lower than that of the commercial PtRu.

[0183] Example 31: PtRuNi / C catalyst

[0184] A catalyst, PtRuNi / C, is prepared by adsorbing H2PtCl6, K2RuCl5·H2O, and K2Ni(CN)4 onto anion exchange resin. The specific preparation process includes the following steps:

[0185] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0186] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 7.38mL of H2PtCl6, 0.1796g of K2RuCl5·H2O and 0.1242g of K2Ni(CN)4 to the solution in sequence, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0187] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0188] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0189] Example 32: PtRuNi / C catalyst

[0190] The difference between Example 32 and Example 31 is that the heat treatment temperature in step (3) is 900℃ and the heat treatment time is 1h.

[0191] Example 33: PtRuNi / C catalyst

[0192] The difference between Example 33 and Example 31 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0193] The TEM image of the PtRuNi / C catalyst prepared above, taking Example 31 as an example, is shown below. Figure 21 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 22 .

[0194] TEM images show that PtRuNi is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtRuNi / C. LSV curves show that the HOR current density of PtRuNi / C is less than 2.5 mA / cm². -2 ECSA calculated based on CO leaching is 25.03 m. 2 / g, the CO desorption peak position is higher than that of the commercial JM PtRu catalyst.

[0195] Example 34: PtRu / C catalyst

[0196] A catalyst PtRu / C is prepared by adsorbing H2PtCl6 and K2RuCl5·H2O onto an anion exchange resin. The specific preparation process includes the following steps:

[0197] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0198] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 7.45mL of H2PtCl6 and 0.1796g of K2RuCl5·H2O to the solution in sequence, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0199] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0200] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0201] Example 35: PtRu / C catalyst

[0202] The difference between Example 35 and Example 34 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0203] Example 36: PtRu / C catalyst

[0204] The difference between Example 36 and Example 34 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0205] The TEM image of the PtRu / C catalyst prepared above, taking Example 34 as an example, is shown below. Figure 23 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 24 .

[0206] TEM images show that PtRu is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtRu / C. LSV curves show that the HOR current density of PtRu / C is less than 2.5 mA / cm². -2 ECSA calculated based on CO leaching is 11.79 m. 2 / g. The CO desorption peak apex position is lower than that of the commercial JM PtRu catalyst.

[0207] Example 37: PtMo / C catalyst

[0208] A catalyst PtMo / C is prepared by adsorbing H2PtCl6 and (NH4)Mo7O using an anion exchange resin. 24 The preparation process for PtMo / C includes the following steps:

[0209] (1) Take resin D301, grind it, and pass it through a 60-mesh sieve;

[0210] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 4.92mL of H2PtCl6 and 0.3951g of (NH4)Mo7O to the solution in sequence. 24 Stir and mix thoroughly, adsorb at 40℃ for 6 hours, and then centrifuge and dry.

[0211] (3) The product obtained in step (2) is placed in a reducing atmosphere for heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and argon, the hydrogen volume content is 20%, the heat treatment temperature is 800℃, and the heat treatment time is 2h.

[0212] (4) The heat-treated material was acid-washed with 1M nitric acid solution at 60°C for 2 hours, then filtered, washed, dried and ground to prepare a fuel cell catalyst with precious metal as the catalytic active component.

[0213] Example 38: PtMo / C catalyst

[0214] The difference between Example 38 and Example 37 is that the heat treatment temperature in step (3) is 900°C and the heat treatment time is 1 hour.

[0215] Example 39: PtMo / C catalyst

[0216] The difference between Example 39 and Example 37 is that the heat treatment temperature in step (3) is 700℃ and the heat treatment time is 3h, while in step (4) a 0.5M sulfuric acid solution is used for pickling, the pickling temperature is 60℃ and the pickling time is 2h.

[0217] The TEM image of the PtMo / C catalyst prepared above, taking Example 37 as an example, is shown below. Figure 25 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 26 .

[0218] TEM images show that PtMo is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtMo / C. LSV curves show that the HOR current density of PtMo / C is less than 2.5 mA / cm². -2 ECSA calculated based on CO leaching is 2.74 m. 2 The CO desorption peak apex position is lower than that of the commercial JM PtRu catalyst.

[0219] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a fuel cell catalyst using a noble metal as the catalytically active component, characterized in that, Includes the following steps: (1) Dissolve the precious metal precursor in water to form a precious metal precursor solution; The precious metal is platinum; (2) The noble metal precursor solution and the carrier precursor are mixed and adsorbed, then centrifuged and dried; the carrier precursor is a macroporous anion exchange resin with tertiary amine group -N(CH3)2. (3) The product obtained from drying in step (2) is heat-treated at 700-900℃ for 1-5 hours under a reducing atmosphere to obtain the product.

2. The method for preparing a fuel cell catalyst with a noble metal as the catalytically active component according to claim 1, characterized in that, Also includes: Add a non-precious metal salt to step (1), wherein the molar ratio of precious metal to non-precious metal is 1-5:1; the non-precious metal is at least one of cobalt, iron, nickel, tin and molybdenum.

3. The method for preparing a fuel cell catalyst with a noble metal as the catalytically active component according to claim 1, characterized in that, In step (3), the reducing atmosphere is a mixture of hydrogen and argon or hydrogen and nitrogen, with a hydrogen volume content of 5-40%.

4. The method for preparing a fuel cell catalyst with a noble metal as the catalytically active component according to claim 1, characterized in that, Also includes: The product obtained in step (3) is pickled. The pickling solution is a 0.5-2M nitric acid or sulfuric acid solution. The pickling temperature is 60-80℃ and the pickling time is 2-10h.

5. A fuel cell catalyst with a noble metal as the catalytic active component, prepared by the preparation method according to any one of claims 1-4.

6. The fuel cell catalyst with noble metal as the catalytic active component according to claim 5, characterized in that, This includes catalysts such as PtCo / C, PtFe / C, PtNi / C, PtPd / C, PtCoAu / C, PtPdAu / C, PtRu / C, PtRuCo / C, PtSnCo / C, Pt-MoC / C, PtRu-MoC / C, PtMo / C, PtRuNi / C, PtRuMoNi / C, and PtRuMo / C.

7. The use of the catalyst according to claim 5 or 6 as a cathode oxygen reduction catalyst for fuel cells or as an anode catalyst for hydrogen hydroxide or direct methanol fuel cells.

8. The use of the catalyst according to claim 5 or 6 in the preparation of fuel cells.

Images