Fuel cell catalysts with anionic resins as carrier precursors, and methods of making and using the same

Abstract

The application discloses a fuel cell catalyst with an anion resin as a carrier precursor and a preparation method and application thereof, and the preparation method comprises the following steps: preparing a metal precursor solution, adding an anion resin into the metal precursor solution for adsorption, performing a first carbonization reduction reaction on the adsorption product, coating the reaction product with silicon dioxide, performing a second carbonization reduction reaction, and finally removing a protective layer and impurities through post-processing, so that more active sites of the catalyst are exposed, and the catalytic performance of the catalyst is improved. The preparation process can control the particle size, uniform distribution of active components and loading capacity of the catalyst, and the operation is simple, the cost is low, and the catalyst can be produced in batches.

Description

Technical Field

[0001] This invention relates to the field of fuel cell catalyst technology, specifically to a fuel cell catalyst using anion exchange resin as a carrier precursor, its preparation method, and its application. Background Technology

[0002] With the development of human society, environmental problems have become increasingly prominent. The environmental crisis is not merely a pollution issue; it stems from an over-reliance on traditional fossil fuels. Therefore, finding new alternative energy sources has become an urgent need to address both the energy and environmental crises. Due to hydrogen's high specific heat capacity, hydrogen energy, using hydrogen as a carrier, is considered an ideal alternative to traditional fuels. As a major application of hydrogen energy, fuel cells have received widespread attention.

[0003] The power generation process of fuel cells requires an electrocatalyst to catalyze the oxidation of hydrogen at the anode and the reduction of oxygen from air at the cathode. Currently, platinum-carbon catalysts remain the best choice for fuel cell electrocatalysts due to their excellent electrocatalytic activity and stability. However, existing platinum-carbon catalysts often use separately added activated carbon powder as a support, and the particle size and distribution are difficult to control effectively. Solving this problem requires specific process equipment and cannot be mass-produced. Summary of the Invention

[0004] To address the aforementioned shortcomings of existing technologies, the present invention aims to provide a fuel cell catalyst with anion exchange resin as a carrier precursor, its preparation method, and its application, thereby solving the problems of existing technologies requiring the separate addition of carbon carriers, difficulty in controlling particle size and distribution, high cost, and inability to mass-produce.

[0005] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A method for preparing a fuel cell catalyst using anion exchange resin as a carrier precursor is provided, comprising the following steps:

[0006] (1) Dissolve the precursors of noble metals and / or co-catalytic metals in water to form a metal precursor solution;

[0007] (2) Add anion exchange resin to the metal precursor solution for adsorption. After adsorption is completed, centrifuge and dry to obtain the adsorbate.

[0008] (3) The adsorbate is subjected to a first heat treatment in a reducing gas atmosphere;

[0009] (4) Disperse the product of the first heat treatment in a solvent, then add a silicon-containing compound and carry out a hydrolysis reaction under alkaline conditions;

[0010] (5) The hydrolysis products are subjected to a second heat treatment under a reducing atmosphere;

[0011] (6) The product of the second heat treatment is post-treated, and finally washed and dried to obtain the final product.

[0012] The beneficial effects of this invention are as follows: Anion exchange resins are readily available, low in cost, porous, and have a large specific surface area, allowing noble metals and co-catalytic metals to be adsorbed on and inside the resin surface. Since the precursors of the noble metals and / or co-catalytic metal components are uniformly dispersed in water, these components can be uniformly adsorbed on and inside the anion exchange resin, thus achieving high metal loading and high dispersion. The amount of anion exchange resin and metal salt used is determined based on the adsorption capacity of the anion exchange resin, and the amount of metal is calculated based on the adsorption charge. During the subsequent heat treatment, the anion exchange resin can form porous carbon, which acts as a support. Therefore, this invention does not require the addition of an additional carbon support. While achieving high metal dispersion and high loading in the resin, the active metal components are ultimately loaded in the form of a support.

[0013] Anion exchange resins contain a significant amount of volatile substances. After the first heat treatment, many of these volatile substances are removed. The product from the first heat treatment is then dispersed in a solvent, and a silicon-containing compound is added. Under alkaline conditions, this compound hydrolyzes to form silica, which coats the adsorbate. The silica-coated catalyst undergoes a second heat treatment. During this second heat treatment, the silica directly restricts the sintering and growth of the adsorbate at high temperatures, allowing for better control of the catalyst particle size and resulting in smaller particles. Finally, a post-treatment process exposes the active components of the catalyst. Smaller particle sizes expose more active sites, thereby improving the catalytic effect.

[0014] The preparation process described above does not require specialized equipment, uses common materials, is low in cost, and does not require the addition of a separate carbon support. Furthermore, the preparation method of this invention can effectively control the particle size and particle size distribution of the catalyst, and can be mass-produced.

[0015] Based on the above technical solution, the present invention can be further improved as follows:

[0016] Furthermore, the precious metal is at least one of gold (Au), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt);

[0017] The co-catalytic metals include at least one of cobalt (Co), iron (Fe), nickel (Ni), tin (Sn), and molybdenum (Mo).

[0018] The beneficial effects of adopting the above-mentioned further technical solution are as follows: when the noble metal precursor is dissolved in water, the noble metal and the above-mentioned co-catalytic metal component can be dissolved in water at a molar ratio of 1:1 to 5:1, according to the needs of the target product, and the concentration of the noble metal reaches 110-130 mmol / L. Preferably, the molar ratio of the noble metal to the co-catalytic metal component is 3:1. Ultrapure water can be selected. Metals are added in the form of salts or acids, i.e., metal precursors. For example, gold is added in the form of chloroauric acid, ruthenium in the form of ammonium hexachlororuthenate, potassium pentachlororuthenate, or potassium hexacyanorhenate, rhodium in the form of sodium rhodium chlorochloroacetate, palladium in the form of potassium chloropalladium, sodium chloropalladium, or 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, or potassium chloroplatinate, cobalt in the form of sodium cobalt cyanide or potassium cobalt cyanide, iron in the form of sodium ferrocyanide, potassium ferrocyanide, or potassium ferrocyanide, nickel in the form of potassium nickel cyanide or potassium hexacyanide, tin in the form of sodium stannate, potassium stannate, or zinc stannate, and molybdenum in the form of ammonium molybdate, sodium molybdate, potassium molybdate, or zinc molybdate.

[0019] Furthermore, in step (2), the adsorption temperature is room temperature - 80℃ and the adsorption time is 4-12h; preferably, the adsorption temperature is 40℃ and the adsorption time is 6h.

[0020] The beneficial effects of adopting the above-mentioned further technical solution are as follows: the adsorption temperature and time affect the adsorption amount. Within a specific temperature range, the higher the temperature, the faster the adsorption rate. However, considering the cost, the preferred adsorption temperature is 40℃ and the adsorption time is 6h.

[0021] Furthermore, the anion exchange 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.

[0022] Furthermore, it also includes: pretreatment of the anion exchange resin, specifically: grinding the anion exchange resin to 30-60 mesh, preferably 60 mesh, with the portion larger than 60 mesh being the pretreated anion exchange resin.

[0023] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: the anion exchange resin can be used directly or after the above-mentioned pretreatment. The pretreated anion exchange resin has a better adsorption effect and can load more metal ions.

[0024] Furthermore, the reducing atmosphere in steps (3) and (5) is a mixture of hydrogen and argon or nitrogen, with a hydrogen volume content of 5-40%, preferably 20%.

[0025] Furthermore, the first heat treatment temperature is 300-550℃, and the heat treatment time is 1-4 hours.

[0026] The beneficial effects of adopting the above-mentioned further technical solution are as follows: during the heat treatment process, more volatile substances in the anion exchange resin can be removed, so that space will not be provided for particle sintering growth in the subsequent second heat treatment process, thus avoiding sintering growth.

[0027] Further, in step (4), the solvent is ethanol, the silicon-containing compound is tetraethyl orthosilicate, silicate, methyl orthosilicate, or APTES, the alkaline conditions are pH = 9-11, the hydrolysis temperature is room temperature - 80℃, and the hydrolysis time is 3-8h; the amount of silicon-containing compound added is 2:1-1:2 in mass ratio of adsorbate to silica. Preferably, the amount of silicon-containing compound added is 1:1 in mass ratio of adsorbate to silica, the alkaline conditions are NH3·H2O solution with pH = 10, the hydrolysis temperature is 60℃, and the hydrolysis time is 6h.

[0028] The beneficial effects of adopting the above-mentioned further technical solution are as follows: This invention uses tetraethyl orthosilicate, silicate, methyl orthosilicate, or APTES as raw materials, ethanol as solvent, and an alkaline solution as a reaction catalyst to hydrolyze the material at room temperature to 80°C for 3-8 hours to prepare silica particles. Ethanol is used as a solvent because it has good miscibility with tetraethyl orthosilicate, and ethanol is inexpensive and non-toxic.

[0029] Furthermore, the second heat treatment temperature is 700-900℃, and the heat treatment time is 6-8h; preferably, the second heat treatment is 800℃, and the heat treatment time is 7h.

[0030] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: hydrogen will improve the catalytic effect of the catalyst. At the same time, under the above-mentioned heat treatment temperature and time conditions, the anion exchange resin of the support precursor can better form a nitrogen-doped porous carbon support. Noble metals and / or co-catalytic metals are loaded on the porous carbon support in the form of elemental metals or intermetallic compounds. Silica will directly restrict the sintering and growth of adsorbates during high temperature. This can better control the particle size of the catalyst and improve the catalytic effect of the catalyst.

[0031] Furthermore, the post-treatment process specifically involves: subjecting the product from the second heat treatment to a hydrothermal reaction in an alkaline solution at a temperature of 80-120°C for 50-70 hours. Preferably, the hydrothermal reaction temperature is 80°C and the reaction time is 60 hours.

[0032] Furthermore, the alkaline solution is a 1-3M sodium hydroxide solution or potassium hydroxide solution; preferably a 2M sodium hydroxide solution.

[0033] Furthermore, the post-treatment process is as follows: the product of the second heat treatment is added to a strong acid solution and stirred at room temperature for 5-12 hours; the strong acid solution is hydrofluoric acid with a concentration of 5-40%, preferably hydrofluoric acid with a concentration of 5%, and stirred at room temperature for 10 hours.

[0034] Furthermore, the post-treatment process specifically involves adding the product from the second heat treatment to a mixed solution of glacial acetic acid, hydrofluoric acid, and ammonium fluoride, and stirring at room temperature for 1-8 hours; wherein the volume ratio of glacial acetic acid, hydrofluoric acid, and ammonium fluoride is 4:1:7; preferably, stirring at room temperature for 6 hours.

[0035] The beneficial effects of adopting the above-mentioned further technical solution are as follows: the purpose of the above post-treatment is to remove the silica protective layer and other impurities, so that the catalyst exposes active sites and improves catalytic performance.

[0036] The fuel cell catalysts prepared by the above preparation method using anion exchange resin as the precursor include: PtCo / C, PtFe / C, PtNi / C, PtPd / C, PtCoAu / C, PtPdAu / C, PtRu / C, PtRuCo / C, PtSnCo / C, Pt-MoC / C, and PtRu-MoC / C.

[0037] In the above catalyst, the active component nanoparticles are 3-5 nm in size, the support is nitrogen-doped porous carbon with a size of 30-1000 nm, the noble metal content is 10-60 wt.%, and the co-catalytic metal content is 1-5 wt.%.

[0038] For example, in PtCo / C, the intermetallic compound formed by PtCo is the active ingredient, and C is the support (the support formed by the resin precursor at the end); in Pt-MoC / C, MoC is a support on which Pt is loaded to form a whole, and then this whole is loaded onto the C support (the support formed by the resin precursor at the end) as the active ingredient.

[0039] The aforementioned fuel cell catalysts using anion exchange resins as precursors can be used as cathode oxygen reduction catalysts in fuel cells, such as PtCo / C, PtFe / C, PtNi / C, PtPd / C, PtCoAu / C, and PtPdAu / C; they can also be used as anode catalysts for hydrogen hydroxide in fuel cells and for direct methanol fuel cells, such as PtRu / C, PtRuCo / C, PtSnCo / C, Pt-MoC / C, and PtRu-MoC / C.

[0040] The present invention has the following beneficial effects:

[0041] This invention employs anion exchange resin to adsorb a metal precursor, followed by a first carbonization-reduction reaction, then silica coating, a second carbonization-reduction reaction, and finally post-treatment to remove the protective layer and impurities. This process exposes more active sites on the catalyst, thereby improving its catalytic performance. The preparation process allows for controllability of catalyst particle size, uniform distribution of active components, and loading, and is simple to operate, low in cost, and suitable for mass production. Attached Figure Description

[0042] Figure 1 This is a TEM image of the PtCo / C catalyst.

[0043] Figure 2 The image shows the XRD pattern and ORR curve of the PtCo / C catalyst.

[0044] Figure 3 This is a TEM image of the PtCo / C catalyst.

[0045] Figure 4 The image shows the XRD pattern and ORR curve of the PtCo / C catalyst.

[0046] Figure 5 The image shows the TEM and mapping of the PtFe / C catalyst.

[0047] Figure 6 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtFe / C catalyst.

[0048] Figure 7 The image shows the TEM and mapping of the catalyst PtSnCo / C.

[0049] Figure 8 The XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtSnCo / C are shown.

[0050] Figure 9 The image shows the TEM and mapping of the catalyst PtCoAu / C.

[0051] Figure 10 The XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtCoAu / C are shown.

[0052] Figure 11 The image shows the TEM and mapping of the catalyst PtPdAu / C.

[0053] Figure 12 XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtPdAu / C.

[0054] Figure 13 The image shows the TEM and mapping of the PtNi / C catalyst.

[0055] Figure 14 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtNi / C catalyst.

[0056] Figure 15 The image shows the TEM and mapping of the PtPd / C catalyst.

[0057] Figure 16 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtPd / C catalyst.

[0058] Figure 17 The image shows the TEM and mapping of the catalyst PtRuMo / C.

[0059] Figure 18 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtRuMo / C.

[0060] Figure 19 The image shows the TEM and mapping of the catalyst PtRuCo / C.

[0061] Figure 20 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtRuCo / C.

[0062] Figure 21 The image shows the TEM and mapping of the catalyst PtRuMoNi / C.

[0063] Figure 22 The XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtRuMoNi / C are shown.

[0064] Figure 23 The image shows the TEM and mapping of the catalyst PtRuNi / C.

[0065] Figure 24 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtRuNi / C.

[0066] Figure 25 The image shows the TEM and mapping of the catalyst PtRu / C.

[0067] Figure 26 The image shows the XRD pattern, LSV curve, and CO dissolution curve of the catalyst PtRu / C.

[0068] Figure 27 The image shows the TEM and mapping of the PtMo / C catalyst.

[0069] Figure 28The image shows the XRD pattern, LSV curve, and CO dissolution curve of the PtMo / C catalyst. Detailed Implementation

[0070] The performance measurement and process involved in this invention are as follows:

[0071] 1. ORR: A three-electrode system was used with a Gamry electrochemical workstation. A glassy carbon electrode loaded with a catalyst was used as the working electrode, saturated Ag / AgCl as the reference electrode, a carbon rod as the counter electrode, and a 0.1M HClO4 solution saturated with N2 or O2 as the electrolyte. First, cyclic voltammetry (CV) was used to activate the electrode for 50 cycles between 0V and 1.2V (relative to the standard hydrogen electrode (vs. RHE)) at a scan rate of 50mV / s. Then, linear voltammetry (LSV) was used at a rotating disk speed of 1600rpm, scanning from 1.1V to 0V and then from 0V to 1.1V, and the potential-current curves were recorded.

[0072] The data processing procedure is as follows: Only the curve from 0V to 1.1V is selected and processed as follows.

[0073] 1) Use the following formula to transform the x-coordinate: E = E c +E Ag / AgCl -IR

[0074] E is the calibrated potential, in volts (V), which is the potential relative to the standard hydrogen electrode; E c It is the recorded potential; E Ag / AgCl I refers to the potential of the Ag / AgCl reference electrode in 0.1M HClO4, which is usually 0.27V; I refers to the recorded current, in amperes (A); R refers to the solution resistance, in ohms (Ω), which is 30Ω in the current test system.

[0075] 2) Use the following formula to convert the modal coordinates J(mA / cm) 2 ) = I * 1000 / S

[0076] J refers to current density, measured in milliamperes per square centimeter (mA / cm²). 2 I refers to the recorded current (as above), in amperes (A); S is the area of ​​the GCE, S equals 0.19625 cm². 2 .

[0077] 2. LSV: In a 0.1M O2-saturated HClO4 solution, at a concentration of 10mV s. -1 The LSV curve was recorded at the scan rate.

[0078] 3. CO: 0.1MN2 in a saturated HClO4 solution at 10mV s -1The scan rate is used to record CO removal.

[0079] 4. 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.

[0080] 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.

[0081] Example 1: Catalyst PtCo / C

[0082] A PtCo / C catalyst is prepared using chloroplatinic acid and potassium cobalt cyanide as metal precursors. The preparation method specifically includes the following steps:

[0083] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0084] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 5.6mL of H2PtCl6 and 0.1821g of K3[Co(CN)6] to the solution, stir and mix evenly, adsorb at 35℃ for 6h and then centrifuge and dry.

[0085] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 400℃, and the heat treatment time was 2h.

[0086] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:0.6, and then add an equal volume of pH=10NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0087] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 900℃, and the heat treatment time is 7h.

[0088] (6) The product of the second heat treatment was added to a 3M NaOH solution and hydrothermally reacted at 80°C for 60 hours. The product was then filtered, washed, dried and ground to obtain the final product.

[0089] Example 2: Catalyst PtCo / C

[0090] The difference between Example 2 and Example 1 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0091] Example 3: Catalyst PtCo / C

[0092] The difference between Example 2 and Example 1 is that the adsorption temperature in step (2) is 60℃ and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550℃ and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900℃ and the heat treatment time is 6h.

[0093] The TEM image of the PtCo / C catalyst prepared above, taking Example 1 as an example, is shown below. Figure 1 XRD patterns and ORR curves can be found in [link to XRD pattern]. Figure 2 TEM results show that the PtCo / C catalyst has good dispersion; XRD pattern shows that the diffraction peaks are consistent with the Pt3Co standard card, indicating that the PtCo / C catalyst was successfully synthesized; ORR curve shows that the half-wave potential is 17 mV higher than that of the Pt / C catalyst.

[0094] Example 4: Catalyst PtCo / C

[0095] A PtCo / C catalyst is prepared using chloroplatinic acid and potassium cobalt cyanide as metal precursors. The preparation method specifically includes the following steps:

[0096] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0097] (2) Take 1g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 5.6mL of H2PtCl6 and 0.1821g of K3[Co(CN)6] to the solution, stir and mix evenly, adsorb at 35℃ for 6h and then centrifuge and dry.

[0098] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0099] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0100] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0101] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0102] Example 5: Catalyst PtCo / C

[0103] The difference between Example 5 and Example 4 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0104] Example 6: Catalyst PtCo / C

[0105] The difference between Example 6 and Example 4 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0106] The TEM image of the PtCo / C catalyst prepared above, taking Example 4 as an example, is shown below. Figure 3 XRD patterns and ORR curves can be found in [link to XRD pattern]. Figure 4 TEM results show that the PtCo / C catalyst has good dispersion; XRD pattern shows that the diffraction peaks shift to higher angles, indicating that Co has entered the Pt lattice and formed a PtCo / C alloy catalyst; ORR curve shows that the half-wave potential is 21 mV higher than that of the Pt / C catalyst.

[0107] Example 7: Catalyst PtFe / C

[0108] A catalyst PtFe / C is prepared using chloroplatinic acid and K3Fe(CN)6 as metal precursors. The preparation method specifically includes the following steps:

[0109] (1) Use MP62 resin after grinding, with a grinding mesh size greater than 60 mesh;

[0110] (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 K3Fe(CN)6 to the solution, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0111] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0112] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0113] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0114] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0115] Example 8: Catalyst PtFe / C

[0116] The difference between Example 8 and Example 7 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0117] Example 9: Catalyst PtFe / C

[0118] The difference between Example 9 and Example 7 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0119] The TEM and mapping images of the PtFe / C catalyst prepared above, taking Example 7 as an example, are shown below. Figure 5 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 6 TEM images show that PtFe is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtFe / C. LSV curves show that the half-wave potential of PtFe / C is 0.891 V. ECSA calculated from CO dissolution is 14.24 m. 2 / g.

[0120] Example 10: Catalyst PtSnCo / C

[0121] A catalyst, PtSnCo / C, is prepared using chloroplatinic acid, K3[Co(CN)6], and K2SnO3 as metal precursors. The preparation method specifically includes the following steps:

[0122] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0123] (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, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0124] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0125] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0126] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0127] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0128] Example 11: Catalyst PtSnCo / C

[0129] The difference between Example 11 and Example 10 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0130] Example 12: Catalyst PtSnCo / C

[0131] The difference between Example 12 and Example 10 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0132] The catalyst PtSnCo / C prepared above, taking Example 10 as an example, its TEM and mapping images are shown below. Figure 7 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 8 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 0.869 V. ECSA calculated from CO dissolution is 17.69 m. 2 / g.

[0133] Example 13: Catalyst PtCoAu / C

[0134] A catalyst, PtCoAu / C, is prepared using chloroplatinic acid, K3[Co(CN)6], and KAuCl4 as metal precursors. The preparation method specifically includes the following steps:

[0135] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0136] (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 KAuCl4 to the solution, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0137] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0138] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0139] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0140] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0141] Example 14: Catalyst PtCoAu / C

[0142] The difference between Example 14 and Example 13 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0143] Example 15: Catalyst PtCoAu / C

[0144] The difference between Example 15 and Example 13 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0145] The catalyst PtCoAu / C prepared above, taking Example 13 as an example, its TEM and mapping images are shown below. Figure 9 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 10 TEM images show that PtCoAu is uniformly dispersed on the support, with a consistent elemental distribution. XRD patterns confirm the successful synthesis of PtCoAu / C. LSV curves show that the half-wave potential of PtCoAu / C is 0.90 V. ECSA calculated from CO dissolution is 15.25 m. 2 / g.

[0146] Example 16: Catalyst PtPdAu / C

[0147] A catalyst PtPdAu / C is prepared using chloroplatinic acid, K2PdCl6, and KAuCl4 as metal precursors. The preparation method specifically includes the following steps:

[0148] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0149] (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 KAuCl4 to the solution, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0150] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0151] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0152] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0153] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0154] Example 17: Catalyst PtPdAu / C

[0155] The difference between Example 17 and Example 16 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0156] Example 18: Catalyst PtPdAu / C

[0157] The difference between Example 18 and Example 16 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0158] The catalyst PtPdAu / C prepared above, taking Example 16 as an example, its TEM and mapping images are shown below. Figure 11 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 12 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 0.867 V. ECSA calculated from CO dissolution is 20.29 m. 2 / g.

[0159] Example 19: Catalyst PtNi / C

[0160] A catalyst PtNi / C is prepared using chloroplatinic acid and K2Ni(CN)4 as metal precursors. The preparation method specifically includes the following steps:

[0161] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[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 6.57mL of H2PtCl6 and 0.154g of K2Ni(CN)4 to the solution, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0163] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0164] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0165] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0166] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0167] Example 20: Catalyst PtNi / C

[0168] The difference between Example 20 and Example 19 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0169] Example 21: Catalyst PtNi / C

[0170] The difference between Example 21 and Example 19 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0171] The TEM and mapping images of the PtNi / C catalyst prepared above, taking Example 19 as an example, are shown below. Figure 13 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 14 TEM images show that PtNi is uniformly dispersed on the support, with a uniform elemental distribution. XRD patterns confirm the successful synthesis of PtNi / C. LSV curves show that the half-wave potential of PtNi / C is 0.868 V. ECSA calculated from CO dissolution is 12.43 m. 2 / g.

[0172] Example 22: Catalyst PtPd / C

[0173] A PtPd / C catalyst is prepared using chloroplatinic acid and K2PdCl6 as metal precursors. The preparation method specifically includes the following steps:

[0174] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0175] (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, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0176] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0177] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0178] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0179] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0180] Example 23: Catalyst PtPd / C

[0181] The difference between Example 23 and Example 22 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0182] Example 24: Catalyst PtPd / C

[0183] The difference between Example 24 and Example 22 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0184] The TEM and mapping images of the PtPd / C catalyst prepared above, taking Example 22 as an example, are shown below. Figure 15 XRD patterns, LSV curves, and CO dissolution curves are shown in [reference needed]. Figure 16 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 from CO dissolution is 12.66 m. 2 / g.

[0185] Example 25: Catalyst PtRuMo / C

[0186] A catalyst, PtRuMo / C, is prepared using chloroplatinic acid, K₂RuCl₅, and (NH₄)Mo₇O as metal precursors. 24 The preparation method specifically includes the following steps:

[0187] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0188] (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. 24 ·4H2O, stir to mix evenly, adsorb at 40℃ for 6 hours, then centrifuge and dry;

[0189] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0190] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0191] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0192] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0193] Example 26: Catalyst PtRuMo / C

[0194] The difference between Example 26 and Example 25 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0195] Example 27: Catalyst PtRuMo / C

[0196] The difference between Example 27 and Example 25 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0197] The catalyst PtRuMo / C prepared above, taking Example 25 as an example, has its TEM and mapping images shown below. Figure 17 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 18 As shown in the figure, the current density for hydrogen hydroxide (HOR) is less than 2.5 mA / cm². -2The CO desorption peak appears earlier than that of the commercial PtRu catalyst, indicating stronger resistance to CO poisoning. The methanol oxidation onset potential of the PtRuMo / C catalyst is lower than that of the commercial JM PtRu catalyst, which is more conducive to methanol oxidation. The If / Ib ratio is higher than that of the commercial JM PtRu (1.46). XRD indicates that the alloying degree is not high.

[0198] Example 28: Catalyst PtRuCo / C

[0199] A catalyst, PtRuCo / C, is prepared using chloroplatinic acid, K2RuCl5, and K3[Co(CN)3] as metal precursors. The preparation method specifically includes the following steps:

[0200] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0201] (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, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0202] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0203] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0204] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0205] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0206] Example 29: Catalyst PtRuCo / C

[0207] The difference between Example 29 and Example 28 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0208] Example 30: Catalyst PtRuCo / C

[0209] The difference between Example 30 and Example 28 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0210] The catalyst PtRuCo / C prepared above, taking Example 28 as an example, has its TEM and mapping images shown below. Figure 19 XRD patterns, LSV curves, and CO dissolution curves are shown in [reference needed]. Figure 20 As shown in the figure, the HOR current density is higher than 2.5 mA / cm². -2 The CO desorption peak appears earlier than that of the commercial PtRu catalyst, indicating stronger resistance to CO poisoning. The methanol oxidation onset potential of the PtRuCo / C catalyst is lower than that of the commercial JM PtRu catalyst, which is more conducive to methanol oxidation. The If / Ib ratio is lower than that of the commercial JM PtRu catalyst, which is more conducive to methanol oxidation. The If / Ib ratio is higher than that of the commercial JM PtRu (1.46). XRD indicates that the alloying degree is not very good.

[0211] Example 31: Catalyst PtRuMoNi / C

[0212] A catalyst, PtRuMoNi / C, is prepared using chloroplatinic acid, K₂RuCl₅, and (NH₄)Mo₇O as metal precursors. 24 The preparation method of K2Ni(CN)4 specifically includes the following steps:

[0213] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0214] (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. 24 Mix 0.071g K2Ni(CN)4 with water, stir until homogeneous, adsorb at 40℃ for 6h, and then centrifuge and dry.

[0215] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0216] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0217] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0218] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0219] Example 32: Catalyst PtRuMoNi / C

[0220] The difference between Example 32 and Example 31 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0221] Example 33: Catalyst PtRuMoNi / C

[0222] The difference between Example 33 and Example 31 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0223] The catalyst PtRuMoNi / C prepared above, taking Example 31 as an example, its TEM and mapping images are shown below. Figure 21 XRD patterns, LSV curves, and CO dissolution curves are shown in [reference needed]. Figure 22 XRD analysis revealed that the PtRuMoNi / C alloy was synthesized; the HOR current density was greater than 2.5 mA cm⁻¹. -2The CO desorption peak position is about 0.5V, which is similar to that of commercial PtRu catalyst (0.5V). The methanol oxidation peak position of PtRuMoNi catalyst is similar to that of commercial PtRu. If / Ib is about 2, which is higher than that of commercial JM PtRu catalyst (1.46).

[0224] Example 34: Catalyst PtRuNi / C

[0225] A catalyst PtRuNi / C is prepared using chloroplatinic acid, K2RuCl5, and K2Ni(CN)4 as metal precursors. The preparation method specifically includes the following steps:

[0226] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0227] (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 H2PtCl6, 0.1796g K2RuCl5·H2O and 0.1242g K2Ni(CN)4 to the solution, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0228] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0229] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0230] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0231] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0232] Example 35: Catalyst PtRuNi / C

[0233] The difference between Example 35 and Example 34 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0234] Example 36: Catalyst PtRuNi / C

[0235] The difference between Example 36 and Example 34 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0236] The catalyst PtRuNi / C prepared above, taking Example 34 as an example, its TEM and mapping images are shown below. Figure 23 XRD patterns, LSV curves, and CO dissolution curves are shown in [reference needed]. Figure 24 XRD results showed that a PtRu / C alloy was synthesized, with a HOR current density of less than 2.5 mA / cm². -2 The CO desorption peak position is higher than that of the commercial JM PtRu catalyst, and the methanol oxidation peak position of the PtRuNi catalyst is higher than that of the commercial PtRu; the If / Ib ratio is about 2, which is higher than that of the commercial PtRu catalyst (1.46).

[0237] Example 37: Catalyst PtRu / C

[0238] A catalyst PtRu / C is prepared using chloroplatinic acid and K2RuCl5·H2O as metal precursors. The preparation method specifically includes the following steps:

[0239] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0240] (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 H2PtCl6 and 0.1796g K2RuCl5·H2O (ruthenium chloride and potassium chloride synthesize ruthenium complex) to the solution, stir and mix evenly, adsorb at 40℃ for 6h and then centrifuge and dry.

[0241] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0242] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0243] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0244] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0245] Example 38: Catalyst PtRu / C

[0246] The difference between Example 38 and Example 37 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0247] Example 39: Catalyst PtRu / C

[0248] The difference between Example 39 and Example 37 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0249] The catalyst PtRu / C prepared above, taking Example 37 as an example, has its TEM and mapping images shown below. Figure 25 XRD pattern, LSV curve, and CO dissolution curve are shown in [reference needed]. Figure 26 XRD analysis showed that a PtRu alloy catalyst was synthesized, with a HOR current density of less than 2.5 mA / cm². -2 The CO desorption peak position (0.43V) is lower than that of the commercial PtRu catalyst (0.5V); the If / Ib ratio is higher than that of the commercial JM PtRu catalyst (1.46V).

[0250] Example 40: Catalyst PtMo / C

[0251] A catalyst PtMo / C is prepared using chloroplatinic acid and (NH4)Mo7O as metal precursors. 24 The preparation method specifically includes the following steps:

[0252] (1) Use resin D301 after grinding, with a grinding mesh size greater than 60 mesh;

[0253] (2) Take 4g of the ground resin D301 and add it to ultrapure water to form a solution of 0.1g / mL. Then add 19.6884mL of H2PtCl6 and 1.5804g of (NH4)Mo7O to the solution. 24 Stir and mix thoroughly, adsorb at 40℃ for 6 hours, and then centrifuge and dry.

[0254] (3) The adsorbate was placed in a reducing atmosphere for the first heat treatment, wherein the reducing atmosphere was a mixture of hydrogen and nitrogen, the hydrogen volume content was 10%, the first heat treatment temperature was 450℃, and the heat treatment time was 2h.

[0255] (4) After grinding the product of the first heat treatment, disperse it in ethanol solvent, add tetraethyl orthosilicate solution at a mass ratio of adsorbate to silica of 1:1, and then add an equal volume of pH=11NH3·H2O solution to carry out hydrolysis reaction. The hydrolysis process is carried out by stirring at 60℃ for 6 hours.

[0256] (5) The hydrolysis product is placed in a reducing atmosphere for a second heat treatment, wherein the reducing atmosphere is a mixture of hydrogen and nitrogen, the hydrogen volume content is 10%, the second heat treatment temperature is 800℃, and the heat treatment time is 7h.

[0257] (6) The product of the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride in a volume ratio of 4:1:7, stirred at room temperature for 6 hours, and then filtered, washed, dried and ground to obtain the final product.

[0258] Example 41: Catalyst PtMo / C

[0259] The difference between Example 41 and Example 40 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 300°C and the heat treatment time is 4h; and the second heat treatment temperature in step (5) is 700°C and the heat treatment time is 8h.

[0260] Example 42: Catalyst PtMo / C

[0261] The difference between Example 42 and Example 40 is that the adsorption temperature in step (2) is 60°C and the adsorption time is 8h; the first heat treatment temperature in step (3) is 550°C and the heat treatment time is 1h; and the second heat treatment temperature in step (5) is 900°C and the heat treatment time is 6h.

[0262] The TEM and mapping images of the PtMo / C catalyst prepared above, taking Example 40 as an example, are shown below. Figure 27 XRD patterns, LSV curves, and CO dissolution curves are shown in [reference needed]. Figure 28 The XRD pattern confirms the successful synthesis of the PtMo alloy catalyst, with a HOR current density greater than 2.5 mA / cm². -2 The onset position of the CO desorption peak is similar to that of the commercial JM PtRu catalyst. The onset potential of the PtRu catalyst is higher than that of the commercial PtRu, indicating that it has weaker resistance to CO poisoning. The If / Ib ratio is higher than that of the commercial JM PtRu catalyst (1.46).

[0263] 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 anion exchange resin as a precursor, characterized in that, Includes the following steps: (1) Dissolve the precursors of noble metals and / or co-catalytic metals in water to form a metal precursor solution; (2) Add anion exchange resin to the metal precursor solution for adsorption. After adsorption is completed, centrifuge and dry to obtain the adsorbate. (3) The adsorbate is subjected to a first heat treatment under a reducing atmosphere; (4) Disperse the product of the first heat treatment in a solvent, then add a silicon-containing compound and carry out a hydrolysis reaction under alkaline conditions; (5) The hydrolysis products are subjected to a second heat treatment under a reducing atmosphere; (6) The product of the second heat treatment is added to an alkaline solution or a strong acid solution or a mixed solution of glacial acetic acid, hydrofluoric acid and ammonium fluoride for post-treatment, and finally washed and dried to obtain the product; The first heat treatment is carried out at a temperature of 300-550℃ for 1-4 hours; the second heat treatment is carried out at a temperature of 700-900℃ for 6-8 hours.

2. The method for preparing a fuel cell catalyst using anion exchange resin as a precursor according to claim 1, characterized in that, The precious metal is at least one of gold, ruthenium, rhodium, palladium, osmium, iridium and platinum; the co-catalytic metal includes at least one of cobalt, iron, nickel, tin and molybdenum.

3. The method for preparing a fuel cell catalyst using anion exchange resin as a precursor according to claim 1, characterized in that, In step (2), the adsorption temperature is room temperature - 80℃ and the adsorption time is 4-12h.

4. The method for preparing a fuel cell catalyst using anion exchange resin as a precursor according to claim 1, characterized in that, The reducing atmosphere in steps (3) and (5) is a mixture of hydrogen and argon or nitrogen, with a hydrogen volume content of 5-40%.

5. The method for preparing a fuel cell catalyst using anion exchange resin as a precursor according to claim 1, characterized in that, In step (4), the solvent is ethanol, the silicon-containing compound is tetraethyl orthosilicate, silicate, methyl orthosilicate or APTES, the alkaline condition is pH=9-11, the hydrolysis temperature is room temperature-80℃, and the hydrolysis time is 3-8h; the amount of silicon-containing compound added is 2:1-1:2 in mass ratio of adsorbate to silica.

6. The method for preparing a fuel cell catalyst using anion exchange resin as a precursor according to claim 1, characterized in that, The post-treatment process specifically involves: subjecting the product from the second heat treatment to a hydrothermal reaction in an alkaline solution at a temperature of 80-120℃ for 50-70 hours; or Add the product from the second heat treatment to a strong acid solution and stir at room temperature for 5-12 hours; or The product from the second heat treatment was added to a mixed solution of glacial acetic acid, hydrofluoric acid, and ammonium fluoride, and stirred at room temperature for 1-8 hours; wherein the volume ratio of glacial acetic acid, hydrofluoric acid, and ammonium fluoride was 4:1:

7.

7. A fuel cell catalyst with an anion exchange resin as a precursor, prepared by the preparation method according to any one of claims 1-6.

8. The fuel cell catalyst using anion exchange resin as a precursor according to claim 7, characterized in that, 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.

9. The application of the fuel cell catalyst with anion exchange resin as a carrier precursor as described in claim 7 or 8 as a fuel cell cathode oxygen reduction catalyst or as a fuel cell hydroxide catalyst.

10. The application of the fuel cell catalyst with an anion exchange resin as a carrier precursor as described in claim 7 or 8 as an anode catalyst for direct methanol fuel cells.

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