A catalyst, its preparation and use

Abstract

The application discloses a kind of catalyst and its preparation method and application, preparation method includes the following steps: (1) soluble metal precursor salt is dissolved in water, then cation resin is added to be adsorbed, after adsorption is completed, it is washed, dried, grinded;(2) the obtained material of step (1) is directly heat-treated in air, heat treatment temperature is 350-650 DEG C, heat treatment time is 4h-12h, then the heat treatment product is washed by acid, washed by water, dried, grinded, and is prepared.The catalyst prepared by the preparation method is a monometallic or multi-metal oxide, with a particle size of 1-20 nm, has a porous structure, can realize low-temperature synthesis of multi-metal oxide during preparation, and is uniformly distributed.The metal oxide can be used as an anode oxygen evolution reaction catalyst for water electrolysis, a cathode oxygen reduction reaction catalyst carrier for fuel cells and an anode anti-reverse catalyst for fuel cells, with high activity and high stability.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a catalyst, its preparation method, and its application. Background Technology

[0002] Hydrogen energy has long been considered the ultimate energy source, and hydrogen production through water electrolysis powered by renewable energy sources such as photovoltaics, wind power, and hydropower is a promising strategy. Currently, the main water electrolysis methods include alkaline water electrolysis and PEM (particulate matter electrolysis). Compared to alkaline water electrolysis, PEM exhibits advantages such as rapid response, flexible load current, and purer hydrogen production. These advantages determine its stronger adaptability to fluctuating renewable energy sources. Therefore, countries around the world are promoting the large-scale application of PEM.

[0003] However, existing PEM electrolysis catalysts for hydrogen production are typically prepared using the following methods: precipitation, sol-gel, microemulsion, hydrothermal, melting, and mixing. These methods suffer from several drawbacks: precise particle size control is difficult, resulting in low activity and stability; the synthesis of multi-metal oxides is challenging, leading to segregation and uneven composition; the processes are complex (including precursor dispersion, stirring, feeding, filtration, washing, high-temperature heat treatment, and pulverization), resulting in high equipment investment and unsuitability for large-scale production. Therefore, developing a low-cost, highly active, and stable anolyte oxygen evolution catalyst is crucial for achieving large-scale PEM hydrogen production. Summary of the Invention

[0004] To address the aforementioned shortcomings of existing technologies, the present invention aims to provide a catalyst, its preparation method, and its application, thereby resolving the problems of high temperature, poor activity and stability in the preparation process of existing PEM water electrolysis hydrogen production catalysts, which are unsuitable for large-scale production.

[0005] The technical solution of the present invention to solve the above-mentioned technical problems is as follows:

[0006] A method for preparing a catalyst includes the following steps:

[0007] (1) Dissolve the required soluble metal precursor salt in water, then add cation resin for adsorption, and after adsorption, wash, dry and grind.

[0008] (2) The product obtained in step (1) is directly heat-treated in air at a temperature of 350-650℃ for 4-12 hours. The heat-treated product is then acid-washed, water-washed, dried, and ground to obtain the final product.

[0009] The beneficial effects of this invention are as follows: Existing catalyst preparation methods mainly employ sol-gel methods and solid-state methods. The sol-gel method often involves uniformly anchoring metal ions within macromolecules, followed by alkaline hydrolysis. The resulting precipitate is then treated at high temperatures to obtain the final product; this method requires temperatures above 650°C. The solid-state method typically involves grinding and dispersing the precursor oxide uniformly, followed by direct high-temperature calcination. Calcination temperatures usually exceed 850°C, and calcination times generally exceed 12 hours, requiring two calcinations to obtain the target product. The mixed oxides obtained by this method are generally very dense, with large particles and no porous structure. The temperatures in the above catalyst preparation methods are all high, and only under high-temperature conditions can the interdiffusion between multiple cations be driven. The technical concept of this invention is to prepare a catalyst by lowering the synthesis temperature without affecting the diffusion between cations.

[0010] In the preparation of the catalyst, a soluble metal cation salt is first dissolved in water, and then a cation exchange resin is added. Through the adsorption of the cation exchange resin, the metal cations are adsorbed onto the resin groups, thus loading the metal cations. The resin loaded with metal cations is then washed, dried, and ground to obtain dry resin particles loaded with metal cations. These particles are then directly heat-treated in air at low temperatures. Following this, an acid washing process removes soluble acidic components, and ultrapure water is used to remove chloride ions or soluble water impurities. Finally, the particles are dried and ground to obtain mono- or multi-component metal oxides. Compared to the high-temperature treatment of existing technologies, this method is much less expensive and can form multi-component metal oxides under low-temperature treatment conditions. The synthesized multi-component metal oxides are uniformly distributed and exhibit good activity and stability. Furthermore, the raw materials used in the preparation process are readily available, low in cost, and the preparation process is simple, making it suitable for large-scale industrial production.

[0011] Furthermore, the various cations adsorbed by the resin are uniformly dispersed within the resin, reducing inter-ionic diffusion during the formation of multi-component oxides. Therefore, pure-phase oxides can be formed at lower temperatures without elemental segregation (the inventors discovered during the research and development process that segregation and uneven atomic diffusion are the main causes of impure phases in multi-component oxides). At low temperatures, the resin carbonizes and combines with oxygen in the air to form carbon dioxide, leaving a porous structure. Additionally, the catalyst is less prone to aggregation at low temperatures.

[0012] The metal precursors are added in the form of the following salts: Ru (ruthenium chloride), Ir (iridium chloride), Pb (lead nitrate, lead chloride, etc.), Ti (titanium trichloride, titanium tetrachloride, titanium iodide, etc.), Sr (strontium sulfate, strontium chloride, strontium nitrate, etc.), Nb (niobium pentachloride, niobium oxalate, etc.), Mo (molybdenum acetylacetonate, etc.), Y (yttrium nitrate, yttrium carbonate, etc.), Zr (zirconium chloride, zirconium sulfate, etc.), Sb (antimony chloride, antimony sulfate, etc.), Ta (tantalum fluoride), La (lanthanum chloride, lanthanum sulfate, lanthanum nitrate, etc.), Ce (cerium chloride, cerium sulfate, cerium nitrate, etc.), Ho (holmium chloride, etc.), Sn (tin tetrachloride, tin sulfate, tin fluoride, etc.). The above are only some of the listed metal precursor salt forms; other anion-formed metal precursor salts are also possible, which are not listed here.

[0013] Furthermore, it also includes a pretreatment process for the cation exchange resin, specifically: the cation exchange resin is ground through a 60-mesh sieve, and the portion larger than 60 mesh is the pretreated cation exchange resin, which is then used in the subsequent adsorption process.

[0014] The beneficial effects of the above-mentioned further technical solutions are as follows: the cation exchange resin can be used directly, or it can be pretreated, such as by grinding and pulverizing it to a mesh size of approximately 60 mesh. After pretreatment, the cation exchange resin can better and more effectively adsorb metal cations, which helps to reduce the amount of resin used.

[0015] Furthermore, in step (1), the weight ratio of cation exchange resin to water is 1-5:20-60.

[0016] The beneficial effects of the above-mentioned further technical solution are as follows: the exchange between cation exchange resin and metal ions occurs not only on the surface of the resin particles, but also largely within the resin particles. Since metal cations are uniformly dispersed in water, and the resin has a strong adsorption effect on metal cations, the metal cations can be uniformly anchored on the resin surface. A weight ratio of cation exchange resin to water of 1-5:20-60 is beneficial for the exchange between cation exchange resin and metal ions. The amount of cation exchange resin and metal salt used is determined based on the adsorption capacity of the cation exchange resin, and the amount of metal is calculated based on the amount of adsorbed charge.

[0017] Furthermore, in step (1), the adsorption temperature is room temperature - 80℃ and the adsorption time is 2-6h; preferably, the adsorption temperature is 40℃ and the adsorption time is 4h.

[0018] The beneficial effects of the above-mentioned further technical solutions are as follows: water temperature can affect the ion exchange rate. When the adsorption temperature is between room temperature and 80°C, it can promote the ion exchange rate and enable metal ions to be rapidly loaded onto the resin.

[0019] Furthermore, in step (2), the heat treatment temperature is 350℃ and the heat treatment time is 6h.

[0020] Furthermore, the acid used in step (2) for pickling is hydrochloric acid or nitric acid, with a concentration of 0.1-2 mol / L, respectively; preferably, the concentration is 1 mol / L. Other acids can also be used for pickling, the purpose of which is to remove impurities that can dissolve the acid.

[0021] Furthermore, in step (2), the pickling temperature is 40-90℃ and the pickling time is 1-8h; preferably, the pickling temperature is 80℃ and the pickling time is 2h.

[0022] The beneficial effect of the above-mentioned further technical solution is that: using hydrochloric acid or nitric acid of a specific concentration for pickling at the above temperature can effectively remove impurities.

[0023] Furthermore, the method also includes the following steps: mixing the product obtained in step (2) with a noble metal salt solution, allowing it to stand, and then annealing it to obtain a supported catalyst; wherein the mass ratio of the product obtained in step (2) to the noble metal in the noble metal salt solution is 1:19-6:4.

[0024] The beneficial effects of the above-mentioned further technical solution are as follows: the metal oxide obtained in step (2) can be used as a carrier to mix with the noble metal salt solution. Because the metal oxide obtained in step (2) has a porous structure, the noble metal salt solution can enter the porous structure. During the standing process, the noble metal salt solution can be completely adsorbed by the metal oxide of the porous structure. Then, after the annealing process, the noble metal salt decomposes and a supported catalyst can be obtained.

[0025] In the above process, the precious metal is added in the form of a precious metal salt solution. The concentration of the precious metal salt solution is determined by the following method: first, determine the mass of the oxide to be added, then determine the water absorption volume at that mass, and then determine the concentration of the precious metal salt based on the required mass of the precious metal and the water absorption volume.

[0026] Further, the product obtained in step (2) is mixed with the precious metal at a mass ratio of 1:9.

[0027] Furthermore, the temperature during the settling process is room temperature - 80℃, and the settling time is 12-24h; preferably, the settling temperature is 30℃ and the settling time is 24h.

[0028] Furthermore, the annealing temperature is 200-500℃, and the annealing time is 3-10h; preferably, the annealing temperature is 400℃, and the annealing time is 7h.

[0029] The catalyst prepared by the above method is a mono- or multi-component metal oxide, wherein the metal is a noble metal and / or a non-noble metal; wherein the particle size of the catalyst is 1-20 nm and has a porous structure.

[0030] The beneficial effects of this invention are as follows: The catalyst in this invention can be any proportion of mono- or multi-component metal oxides, such as mono-noble metal oxides, multi-component noble metal oxides, or oxides formed from noble metals and non-noble metals. This catalyst has a small particle size and a porous structure, which allows it to combine with more reactant molecules, effectively enhancing the catalyst's activity and improving its vitality.

[0031] Based on the above technical solution, the present invention can be further improved as follows:

[0032] Furthermore, the metal in the above catalyst is at least one selected from Ru, Ir, Pb, Ti, Y, Sn, Sr, Ta, Sb, La, Zr, Mo, Nb, Ho, and Ce.

[0033] Furthermore, the catalysts mentioned above are RuO2, IrO2, and Ru. x Ir 1-x O2, Pb2Ru2O 6.5 Ru x Ti 1-x O2, Y2Ir2O 6.5 Ru x Sn 1-x O2, Pt / Ru x Ti 1-x O2, Sr x Ru y Ir 1-x-y O2, Ru x Ir y Ta 1-x-y O2, Ru x Sn y Sb z Ta 1-x-y-z O2, Ru x Ir y La z Zr m Mo 1-x-y-z-m O2, Ir x Sn y Sb z Ta m Nb 1-x-y-z-m O2, Ho x Nb y Ru m Ir 1-x-y-m O2, Y x La y Ce m Ru n Ir 1-x-y-m-n O2.

[0034] In the above compounds, the subscript letters of each element represent the molar ratio of different atoms, such as Ru. x Ir 1-x In O2, 0 ≤ x ≤ 1, 0 ≤ 1 - x ≤ 1; Ru x Ti 1-x In O2, 0 ≤ x ≤ 1, 0 ≤ 1 - x ≤ 1; Ru x Sn 1-x In O2, 0 ≤ x ≤ 1, 0 ≤ 1 - x ≤ 1; Pt / Ru x Ti 1- x In O2, 0 ≤ x ≤ 1, 0 ≤ 1 - x ≤ 1; Sr x Ru y Ir 1-x-y In O2, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, and 0 ≤ 1 - xy ≤ 1; Ru x Ir y Ta 1-x-y In O2, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, and 0 ≤ 1 - xy ≤ 1; Ru x Sn y Sb z Ta 1-x-y-z In O2, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, and 0 ≤ 1 - xyz ≤ 1; Ru x Ir y La z Zr m Mo 1-x-y-z-m In O2, 0≤x≤1, 0≤y≤1, 0≤z≤1, 0≤m≤1, 0≤1-xyzm≤1; Ir x Sn y Sb z Ta m Nb 1-x-y-z-m In O2, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, 0 ≤ m ≤ 1, 0 ≤ 1 - xyzm ≤ 1; Ho x Nb y Ru m Ir 1-x-y-m In O2, 0≤x≤1, 0≤y≤1, 0≤m≤1, 0≤1-xym≤1; Y x La y Ce m Ru n Ir 1-x-y-m-n In O2, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ m ≤ 1, 0 ≤ n ≤ 1, and 0 ≤ 1 - xymn ≤ 1.

[0035] The above catalysts are used as catalysts for oxygen evolution reaction at the anode in water electrolysis, catalyst supports for oxygen reduction reaction at the cathode in fuel cells, and anti-reverse electrode catalysts at the anode in fuel cells.

[0036] Furthermore, RuO2, IrO2, Ru x Ir 1-x O2, Pb2Ru2O 6.5 Ru x Ti 1-x O2, Y2Ir2O 6.5 Ru x Sn 1-x O2, Sr x Ru y Ir 1-x-y O2, Ru x Ir y Ta 1-x-y O2, Ru x Sn y Sb z Ta 1-x-y-z O2, Ru x Ir y La z Zr m Mo 1-x-y-z-m O2, Ir x Sn y Sb z Ta m Nb 1-x-y-z-m O2, Ho x Nb y Ru m Ir 1-x-y-m O2, Y x La y Ce m Ru n Ir 1-x-y-m-n O2 can be used as a catalyst for the oxygen evolution reaction at the anode of water electrolysis; Ru x Ti 1-x O2 can be used as a catalyst support for the oxygen reduction reaction at the cathode of fuel cells, Ru x Ti 1- x O2 acts as a carrier to load Pt, resulting in Pt / Ru. x Ti 1-x O2 can also be used as a carrier; Pb2Ru2O 6.5 IrO2, Ir x Sn y Sb z Ta m Nb 1-x-y-z-m O2 can also be used as an anode anti-reverse catalyst for fuel cells.

[0037] The present invention has the following beneficial effects:

[0038] The metal oxide particles of the present invention are smaller and have a porous structure. During the preparation process, multi-element metal oxides can be synthesized at low temperature and are uniformly distributed. The metal oxides can be used as catalysts for oxygen evolution reaction at the anode of water electrolysis, catalyst supports for oxygen reduction reaction at the cathode of fuel cells, and anti-reverse electrode catalysts at the anode of fuel cells, exhibiting high activity and high stability.

[0039] The following uses Pb2Ru2O 6.5 For example, the corresponding synthesis principle diagram is given; see [link / reference]. Figure 24 .

[0040] The above synthesis process includes the following aspects:

[0041] (1) Resin dissociation: Cationic resins will dissociate into H+ in aqueous solution. + Ions, the resin body due to the loss of H + Ions carry a negative charge;

[0042] (2) Resin adsorption: Negatively charged resins can adsorb cations in solution due to Coulomb interactions;

[0043] (3) Annealing: During the annealing process, the resin after adsorbing cations undergoes two steps: 1) The resin gradually carbonizes and combines with oxygen in the air to generate carbon dioxide, leaving a porous structure; 2) The metal cations are also gradually oxidized to form oxides. Attached Figure Description

[0044] Figure 1 The catalyst Pb2Ru2O prepared in Example 1 6.5 Structural characterization map.

[0045] Figure 2 The image shows the structural characterization of the catalyst RuO2 prepared in Example 4.

[0046] Figure 3 The image shows the structural characterization of the catalyst IrO2 prepared in Example 7.

[0047] Figure 4 The catalyst Ir prepared in Example 10 0.3 Ru 0.7 Structural characterization map of O2.

[0048] Figure 5 The catalyst Ru prepared in Example 13 0.7 Sn 0.3 Structural characterization map of O2.

[0049] Figure 6 The catalyst Pt / Ru prepared in Example 16 0.7 Ti 0.3 Structural characterization map of O2.

[0050] Figure 7 The catalyst Sr prepared in Example 17 0.5 Ru 0.4375 Ir 0.0625 Structural characterization map of O2.

[0051] Figure 8 The catalyst Ho prepared in Example 20 0.1 Nb 0.1 Ru 0.7 Ir 0.1 Structural characterization map of O2.

[0052] Figure 9 The catalyst La prepared in Example 23 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 Structural characterization map of O2.

[0053] Figure 10 The catalyst Sr prepared in Example 26 0.2 Ru 0.4 Ir 0.4 X-ray diffraction pattern of O2.

[0054] Figure 11 The catalyst Sr of this invention 0.2 Ru 0.4 Ir 0.4 The OER performance test results of O2; the curves in the figure, from left to right, represent the catalyst Sr of this invention. 0.2 Ru 0.4 Ir 0.4 O2, commercial RuO2, commercial IrO2.

[0055] Figure 12 The catalyst of this invention is Pb2Ru2O 6.5 The OER performance test results; where the curves in the figure, from left to right, represent the catalyst Pb2Ru2O of this invention. 6.5 Commercial RuO2.

[0056] Figure 13 The figure shows the OER performance test results of the catalyst RuO2 of this invention; the curves in the figure, from left to right, represent the catalyst RuO2 of this invention and commercial RuO2.

[0057] Figure 14 The figure shows the OER performance test results of the catalyst IrO2 of this invention; the curves in the figure, from left to right, represent the catalyst IrO2 of this invention and commercial IrO2.

[0058] Figure 15The catalyst Ru of this invention 0.7 Sn 0.3 The OER performance test results of O2; the curves in the figure, from left to right, represent the catalyst Ru of this invention. 0.7 Sn 0.3 O2, commercial RuO2.

[0059] Figure 16 The catalyst Sr of this invention 0.5 Ru 0.4375 Ir 0.0.0625 The OER performance test results of O2; the curves in the figure, from left to right, represent the catalyst Sr of this invention. 0.5 Ru 0.4375 Ir 0.0.0625 O2, commercial RuO2, commercial IrO2.

[0060] Figure 17 The catalyst Ho of this invention 0.1 Nb 0.1 Ru 0.7 Ir 0.1 The OER performance test results of O2; the curves in the figure, from left to right, represent the catalyst Ho of this invention. 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2, commercial RuO2, commercial IrO2.

[0061] Figure 18 The catalyst La of this invention 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 The OER performance test results of O2; the curves in the figure, from left to right, represent the catalyst La of this invention. 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2, commercial RuO2, commercial IrO2.

[0062] Figure 19 The catalyst of this invention is Pt / Ru 0.7 Ti 0.3 ORR performance test results for O2.

[0063] Figure 20 The catalyst of this invention is Pt / Ru 0.7 Ti 0.3 ORR performance test results after aging O2 at 1.5V for 3 hours.

[0064] Figure 21The ORR performance test results are for a commercial Pt / C catalyst aged at 1.5V for 3 hours.

[0065] Figure 22 The results show the reverse polarity performance of the Pt / C catalyst of this invention.

[0066] Figure 23 The catalyst of this invention is Pb2Ru2O 6.5 Reverse polarity test results of (10wt%)+Pt / C.

[0067] Figure 24 Pb2Ru2O 6.5 The principle diagram of the synthesis. Detailed Implementation

[0068] The cation exchange resins used in this invention include: 001×7Na(732), 002×7, 001×10(002SC), 001×81, D113, D131, D001, D254, D61, and D85. In addition, the following cation exchange resins can also be used: 001×4(734), D002, D204, and D62.

[0069] 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.

[0070] Example 1: Pb2Ru2O 6.5 catalyst

[0071] A catalyst Pb2Ru2O 6.5 The preparation method involves using a cation exchange resin to adsorb PbCl2 (lead chloride) and RuCl3 (ruthenium trichloride) to prepare Pb2Ru2O. 6.5 The specific preparation process of pyrochlore includes the following steps:

[0072] (1) Clean the cation resin D113 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0073] (2) Dissolve the metal precursors PbCl2 (lead chloride, 0.5 mmol, 139 mg) and RuCl3 (ruthenium trichloride, 0.25 mmol, 52 mg) in 20 mL of ultrapure water, then add 1 g of ground cation exchange resin, adsorb at 40 °C for 6 h, wash and dry after adsorption, and grind into powder.

[0074] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0075] (4) The heat-treated material is acid-washed with 40 mL of 1 mol / L nitric acid solution in a water bath to remove the lead oxides that have not formed a phase. Then it is washed until neutral, dried, ground and obtained. The water bath temperature is 90℃ and the water bath time is 1 h.

[0076] Example 2: Pb2Ru2O 6.5 catalyst

[0077] A catalyst Pb2Ru2O 6.5 The preparation method involves using a cation exchange resin to adsorb PbCl2 (lead chloride) and RuCl3 (ruthenium trichloride) to prepare Pb2Ru2O. 6.5 The specific preparation process of pyrochlore includes the following steps:

[0078] (1) Clean the cation resin D113 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0079] (2) Dissolve the metal precursors PbCl2 (lead chloride, 0.75 mmol, 210 mg) and RuCl3 (ruthenium trichloride, 0.5 mmol, 104 mg) in 40 mL of ultrapure water, then add 3 g of ground cation exchange resin, adsorb at room temperature for 6 h, wash and dry after adsorption, and grind into powder.

[0080] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 4 hours;

[0081] (4) The heat-treated material was acid-washed with 40 mL of 0.1 mol / L nitric acid solution in a water bath to remove the lead oxides that had not formed a phase. Then it was washed until neutral, dried, and ground to obtain the product. The water bath temperature was 40℃ and the water bath time was 8 h.

[0082] Example 3: Pb2Ru2O 6.5 catalyst

[0083] A catalyst Pb2Ru2O 6.5 The preparation method involves using a cation exchange resin to adsorb PbCl2 (lead chloride) and RuCl3 (ruthenium trichloride) to prepare Pb2Ru2O. 6.5 The specific preparation process of pyrochlore includes the following steps:

[0084] (1) Clean the cation resin D113 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0085] (2) Dissolve the metal precursors PbCl2 (lead chloride, 0.75 mmol; 210 mg) and RuCl3 (ruthenium trichloride, 0.25 mmol; 52 mg) in 60 mL of ultrapure water, then add 5 g of ground cation exchange resin, adsorb at 80 °C for 2 h, wash and dry after adsorption, and grind into powder.

[0086] (3) The product obtained in step (2) is directly heat-treated in air at 500°C for 8 hours;

[0087] (4) The heat-treated material is acid-washed with 20 mL of 2 mol / L nitric acid solution in a water bath to remove the lead oxides that have not formed a phase. Then it is washed until neutral, dried, ground and obtained. The water bath temperature is 60℃ and the water bath time is 3h.

[0088] The catalyst Pb2Ru2O prepared above 6.5 Taking Example 1 as an example, its structural characterization diagram is shown below. Figure 1 ,in, Figure 1-1 Pb2Ru2O 6.5 X-ray diffraction pattern, Figure 1-2 Pb2Ru2O 6.5 High-magnification transmission electron microscopy image, Figure 1-3 This represents the annular dark field and elemental energy spectrum. Figure 1-1 The XRD results showed that it was similar to Pb2Ru2O 6.5 The results corresponding to the standard card (PDF card) indicate that the synthesized phase is Pb2Ru2O. 6.5 .

[0089] Figure 1-2 The results show that Pb2Ru2O 6.5 It consists of tiny nanocrystals of about 3 nm and has a porous structure. Figure 1-3 The top left of the image shows a ring-shaped dark-field plot, with Pb (top right), Ru (bottom left), and O (bottom right). This indicates that Pb, Ru, and O are uniformly distributed in the sample.

[0090] Example 4: RuO2 catalyst

[0091] A catalyst RuO2, the preparation method of which includes the following steps:

[0092] (1) Clean the cation resin 001×7Na(732) with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0093] (2) Dissolve the metal precursor RuCl3 (ruthenium trichloride, 204 mg) in 40 mL of ultrapure water, then add 5 g of ground cation resin, adsorb at room temperature for 4 h, wash and dry after adsorption, and grind into powder.

[0094] (3) The product obtained in step (2) is directly heat-treated in air at 450°C for 8 hours;

[0095] (4) The heat-treated material is acid-washed with 40 mL of 1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, ground, and obtained; wherein the water bath temperature is 90℃ and the water bath time is 2 h.

[0096] Example 5: RuO2 catalyst

[0097] A catalyst RuO2, the preparation method of which includes the following steps:

[0098] (1) Clean the cation resin 001×7Na(732) with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0099] (2) Dissolve the metal precursor RuCl3 (ruthenium trichloride, 68 mg) in 40 mL of ultrapure water, then add 1 g of ground cation resin, adsorb at 80 °C for 2 h, wash and dry after adsorption, and grind into powder.

[0100] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 4 hours;

[0101] (4) The heat-treated material is acid-washed with 40 mL of 0.1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 40℃ and the water bath time is 8 h.

[0102] Example 6: RuO2 catalyst

[0103] A catalyst RuO2, the preparation method of which includes the following steps:

[0104] (1) Clean the cation resin 001×7Na(732) with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0105] (2) Dissolve the metal precursor RuCl3 (ruthenium trichloride, 136 mg) in 60 mL of ultrapure water, then add 3 g of ground cation resin, adsorb at 60 °C for 3 h, wash and dry after adsorption, and grind into powder.

[0106] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0107] (4) The heat-treated material is acid-washed with 20 mL of 2 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 60℃ and the water bath time is 4 h.

[0108] The structure characterization spectrum of the catalyst RuO2 prepared above, taking Example 4 as an example, is shown in the figure above. Figure 2 ,in, Figure 2-1 The X-ray diffraction patterns of RuO2 and commercial RuO2 are shown below. Figure 2-2 The present invention is Pb2Ru2O 6.5 High-magnification transmission electron microscopy image, Figure 1-3 This represents the annular dark field and elemental energy spectrum. Figure 2-1 The XRD results showed results corresponding to the RuO2 standard card (PDF card), indicating that the synthesized phase was RuO2. Figure 2-2 The results show that RuO2 is composed of tiny nanoparticles of about 5 nm and has a porous structure. Figure 2-3 The top left is a ring-shaped dark field image. Ru (top right) and O (bottom left) indicate that Ru and O are uniformly distributed in the sample.

[0109] Example 7: IrO2 catalyst

[0110] A catalyst IrO2, the preparation method of which includes the following steps:

[0111] (1) Clean the cation resin D001 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0112] (2) Dissolve the metal precursor IrCl3 (iridium chloride, 60mg) in 40mL of ultrapure water, then add 3g of ground cation resin, adsorb at 80℃ for 2h, wash and dry after adsorption, and grind into powder.

[0113] (3) The product obtained in step (2) is directly heat-treated in air at 550°C for 6 hours;

[0114] (4) The heat-treated material is acid-washed with 20 mL of 0.1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 50℃ and the water bath time is 3 h.

[0115] Example 8: IrO2 catalyst

[0116] A catalyst IrO2, the preparation method of which includes the following steps:

[0117] (1) Clean the cation resin D001 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0118] (2) Dissolve the metal precursor IrCl3 (iridium chloride, 30 mg) in 20 mL of ultrapure water, add 1 g of ground cation resin, adsorb at room temperature for 6 h, wash and dry after adsorption, and grind into powder.

[0119] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0120] (4) The heat-treated material is acid-washed with 40 mL of 1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, ground, and obtained; wherein the water bath temperature is 40℃ and the water bath time is 8 h.

[0121] Example 9: IrO2 catalyst

[0122] A catalyst IrO2, the preparation method of which includes the following steps:

[0123] (1) Clean the cation resin D001 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0124] (2) Dissolve the metal precursor IrCl3 (iridium chloride, 90mg) in 40mL of ultrapure water, then add 5g of ground cation resin, adsorb at 80℃ for 2h, wash and dry after adsorption, and grind into powder.

[0125] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 4 hours;

[0126] (4) The heat-treated material is acid-washed with 40 mL of 2 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 90℃ and the water bath time is 1 h.

[0127] The structure characterization spectrum of the catalyst IrO2 prepared above, taking Example 7 as an example, is shown in the figure above. Figure 3 ,in, Figure 3-1 The X-ray diffraction pattern of IrO2. Figure 3-2 This is a high-magnification transmission electron microscope image of IrO2. Figure 3-3 This represents the annular dark field and elemental energy spectrum. Figure 3-1 The XRD results showed a correlation with the IrO2 standard card (PDF card), indicating that the synthesized phase was IrO2. Figure 3-2 The results show that IrO2 is composed of tiny nanoparticles of about 8 nm and has a porous structure. Figure 3-3 The top left is a ring-shaped dark field image. Pb (top right), Ir (bottom left), and O (bottom right) indicate that the three elements Ir and O are uniformly distributed in the sample.

[0128] Example 10: Ir 0.3 Ru 0.7 O2 catalyst

[0129] A catalyst Ir 0.3 Ru 0.7 O2, the preparation method of which includes the following steps:

[0130] (1) Clean the cation resin 002×7 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0131] (2) Take metal precursors IrCl3 (iridium chloride, 0.22 mmol, 65.4 mg) and RuCl3 (ruthenium chloride, 0.5 mmol, 105 mg) and dissolve them in 60 mL of ultrapure water. Then add 5 g of ground cation exchange resin and adsorb at 50 °C for 6 h. After adsorption is complete, wash, dry and grind into powder.

[0132] (3) The product obtained in step (2) is directly heat-treated in air at 500°C for 10 hours;

[0133] (4) The heat-treated material is acid-washed with 10 mL of 2 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 70℃ and the water bath time is 8h.

[0134] Example 11: Ir 0.3 Ru0.7 O2 catalyst

[0135] A catalyst Ir 0.3 Ru 0.7 O2, the preparation method of which includes the following steps:

[0136] (1) Clean the cation resin 002×7 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0137] (2) Take metal precursors IrCl3 (iridium chloride, 0.22 mmol, 65.4 mg) and RuCl3 (ruthenium chloride, 0.5 mmol, 105 mg) and dissolve them in 20 mL of ultrapure water. Then add 1 g of ground cation exchange resin and adsorb at room temperature for 6 h. After adsorption is complete, wash and dry the resin and grind it into powder.

[0138] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0139] (4) The heat-treated material is acid-washed with 10 mL of 1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 40℃ and the water bath time is 8h.

[0140] Example 12: Ir 0.3 Ru 0.7 O2 catalyst

[0141] A catalyst Ir 0.3 Ru 0.7 O2, the preparation method of which includes the following steps:

[0142] (1) Clean the cation resin 002×7 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0143] (2) Take metal precursors IrCl3 (iridium chloride, 0.22 mmol, 65.4 mg) and RuCl3 (ruthenium chloride, 0.5 mmol, 105 mg) and dissolve them in 40 mL of ultrapure water. Then add 3 g of ground cation exchange resin and adsorb at 80 °C for 2 h. After adsorption is complete, wash, dry and grind into powder.

[0144] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 4 hours;

[0145] (4) The heat-treated material is acid-washed with 40 mL of 0.1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 90℃ and the water bath time is 1 h.

[0146] The catalyst Ir prepared above 0.3 Ru 0.7 O2, taking Example 10 as an example, its structural characterization diagram is shown below. Figure 4 ,in, Figure 4-1 For Ir 0.3 Ru 0.7 X-ray diffraction pattern of O2 Figure 4-2 For Ir 0.3 Ru 0.7 High-magnification transmission electron microscope image of O2. Figure 4-3 This represents the annular dark field and elemental energy spectrum. Figure 4-1 The XRD results showed results corresponding to the RuO2 or IrO2 standard cards (PDF cards). This is because the crystal structures of RuO2 and IrO2 are almost identical, indicating that the synthesized phase is still of the RuO2 type. Figure 4-2 The results showed that Ir 0.3 Ru 0.7 O2 is composed of tiny nanoparticles of about 5 nm and has a porous structure. Figure 4-3 The top left is a ring-shaped dark field image. Ru (top right), Ir (bottom left), and O (bottom right) indicate that the three elements Ir, Ru, and O are uniformly distributed in the sample.

[0147] Example 13: Ru 0.7 Sn 0.3 O2 catalyst

[0148] A catalyst Ru 0.7 Sn 0.3 O2, the preparation method of which includes the following steps:

[0149] (1) Clean the cation resin 001×10 (002SC) with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0150] (2) Take the metal precursor RuCl3 (ruthenium chloride, 0.5 mmol, 105 mg) and SnCl4·5H2O (tin chloride pentahydrate, 0.22 mmol, 75.2 mg) and dissolve them in 50 mL of ultrapure water. Then add 3 g of the ground cation exchange resin and adsorb it at 30 °C for 5 h. After the adsorption is complete, wash and dry it and grind it into powder.

[0151] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 10 hours;

[0152] (4) The heat-treated material is acid-washed with 30 mL of 0.5 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 60℃ and the water bath time is 7 h.

[0153] Example 14: Ru 0.7 Sn 0.3 O2 catalyst

[0154] A catalyst Ru 0.7 Sn 0.3 O2, the preparation method of which includes the following steps:

[0155] (1) Clean the cation resin 001×10 (002SC) with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0156] (2) Take the metal precursor RuCl3 (ruthenium chloride, 0.5 mmol, 105 mg) and SnCl4·5H2O (tin chloride pentahydrate, 0.22 mmol, 75.2 mg) and dissolve them in 20 mL of ultrapure water. Then add 1 g of the ground cation resin and adsorb it at room temperature for 6 h. After the adsorption is complete, wash and dry it and grind it into powder.

[0157] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0158] (4) The heat-treated material is acid-washed with 10 mL of 2 mol / L nitric acid solution in a water bath, then washed until neutral, dried, ground, and obtained; wherein the water bath temperature is 40℃ and the water bath time is 8h.

[0159] Example 15: Ru 0.7 Sn 0.3 O2 catalyst

[0160] A catalyst Ru 0.7 Sn 0.3 O2, the preparation method of which includes the following steps:

[0161] (1) Clean the cation resin 001×10 (002SC) with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0162] (2) Take the metal precursor RuCl3 (ruthenium chloride, 0.5 mmol, 105 mg) and SnCl4·5H2O (tin chloride pentahydrate, 0.22 mmol, 75.2 mg) and dissolve them in 60 mL of ultrapure water. Then add 5 g of the ground cation exchange resin and adsorb at 80 °C for 2 h. After the adsorption is complete, wash and dry the resin and grind it into powder.

[0163] (3) The product obtained in step (2) is directly heat-treated in air at 500°C for 8 hours;

[0164] (4) The heat-treated material is acid-washed with 40 mL of 0.1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain the product; wherein the water bath temperature is 90℃ and the water bath time is 1 h.

[0165] The catalyst Ru obtained above 0.7 Sn 0.3 O2, taking Example 13 as an example, its structural characterization diagram is shown below. Figure 5 ,in, Figure 5-1 For Ru 0.7 Sn 0.3 X-ray diffraction pattern of O2 Figure 5-2 For Ru 0.7 Sn 0.3 High-magnification transmission electron microscope image of O2. Figure 5-3 This represents the annular dark field and elemental energy spectrum. Figure 5-1 The XRD results showed results corresponding to the RuO2 standard card (PDF card). This is because the doping of Sn did not change the RuO2 crystal structure, indicating that the synthesized phase is still of the RuO2 type. Figure 5-2 The results show that Ru 0.7 Sn 0.3 O2 is composed of tiny nanoparticles of about 5 nm and has a porous structure. Figure 5-3 The top left is a ring-shaped dark field image. Sn (top right), Ru (bottom left), and O (bottom right) indicate that the three elements Sn, Ru, and O are uniformly distributed in the sample.

[0166] Example 16: Pt / Ru 0.7 Ti 0.3 O2 catalyst

[0167] A catalyst Pt / Ru 0.7 Ti 0.3 O2, the preparation method of which includes the following steps:

[0168] (1) Clean the cation resin D131 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0169] (2) Take the metal precursor RuCl3 (ruthenium chloride, 0.5 mmol, 105 mg) powder and TiCl3 liquid (137.14 mg, Ti content 17.5 wt%) and dissolve them in 40 mL of ultrapure water. Then add 3 g of ground cation resin and adsorb at 30 °C for 5 h. After adsorption is complete, wash and dry the product and grind it into powder.

[0170] (3) The product obtained in step (2) is directly heat-treated in air at 450°C for 10 hours;

[0171] (4) The heat-treated material was acid-washed with 30 mL of 0.5 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Ru. 0.7 Ti 0.3 O2; wherein, the water bath temperature is 60℃ and the water bath time is 7h;

[0172] (5) Ru 0.7 Ti 0.3 O2 is mixed with chloroplatinic acid solution, and after standing in a constant temperature oven at 30℃ for 24 hours, it is annealed at 400℃ for 7 hours to obtain the product; wherein, Pt and Ru 0.7 Ti 0.3 The mass ratio of O2 is 1:9.

[0173] The concentration of the above chloroplatinic acid is determined by Ru 0.7 Ti 0.3 The volume of water absorbed by O2 is determined by both the amount of Pt loaded. First, determine a certain mass of Ru... 0.7 Ti 0.3 The amount of undiluted chloroplatinic acid is determined by the water absorption volume of O2 and the mass of the loaded Pt metal, i.e., the preparation of 10% Pt / Ru 0.7 Ti 0.3 The specific process of O2 catalyst is as follows:

[0174] First, determine the water absorption volume: Weigh 59 mg of Ru 0.7 Ti 0.3 O2 was used to determine that its water absorption volume was 0.5 mL;

[0175] Prepare a chloroplatinic acid solution of a certain concentration according to the above-mentioned water absorption volume and the expected Pt loading mass, that is, prepare a solution of 11.8 mg / mL.

[0176] Weigh out 59mg of Ru 0.7 Ti 0.3 O2 was added to 0.5 mL of the prepared chloroplatinic acid solution, and the mixture was allowed to stand in a constant temperature oven at 30°C for 24 h, followed by annealing at 400°C for 7 h to obtain the final product.

[0177] The catalyst Pt / Ru prepared above 0.7 Ti 0.3 O2, its structural characterization spectrum is shown in Figure 6 ,in, Figure 6-1 For Pt / Ru 0.7 Ti 0.3 X-ray diffraction pattern of O2 Figure 6-2 For Pt / Ru 0.7 Ti 0.3 High-magnification transmission electron microscope image of O2. Figure 6-3 This represents the annular dark field and elemental energy spectrum. Figure 6-1 The XRD results showed correspondence with those of the RuO2 and Pt standard cards (PDF cards). This is because the doping of Ti did not change the crystal structure of RuO2 and Pt was successfully loaded with Ru. 0.7 Ti 0.3 The presence of O2 indicates that the synthesized phase has a RuO2-type structure and the presence of metallic Pt. Figure 6-2 The results show that the one with diffraction fringes is Ru. 0.7 Ti 0.3 O2, and the darker-colored particles are metallic Pt. Figure 6-3 The top left of the image shows a ring-shaped dark-field plot, with Ti (top center), Ru (top right), Pt (bottom left), and O (bottom center). This indicates that Ti, Ru, and O are uniformly distributed in the sample, but Pt is loaded onto Ru in the form of particles. 0.7 Ti 0.3 O2 on.

[0178] Example 17: Sr 0.5 Ru 0.4375 Ir 0.0625 O2 catalyst

[0179] A catalyst Sr 0.5 Ru 0.4375 Ir 0.0625 O2, the preparation method of which includes the following steps:

[0180] (1) Clean the cation resin D001 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0181] (2) Dissolve the metal precursors SrCl2·6H2O (strontium chloride hexahydrate, 228 mg), RuCl3 (ruthenium chloride, 52 mg) and IrCl3 (iridium chloride, 10.6 mg) powder in 50 mL of ultrapure water, then add 3 g of ground cation exchange resin, adsorb at 40 °C for 6 h, after adsorption is complete, wash and dry, and grind into powder;

[0182] (3) The product obtained in step (2) is directly heat-treated in air at 450°C for 8 hours;

[0183] (4) The heat-treated material was acid-washed with 40 mL of 1 mol / L hydrochloric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Sr. 0.5 Ru 0.4375 Ir 0.0625 O2; wherein, the water bath temperature is 60℃ and the water bath time is 2h.

[0184] Example 18: Sr 0.5 Ru 0.4375 Ir 0.0625 O2 catalyst

[0185] A catalyst Sr 0.5 Ru 0.4375 Ir 0.0625 O2, the preparation method of which includes the following steps:

[0186] (1) Clean the cation resin D001 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0187] (2) Dissolve the metal precursors SrCl2·6H2O (strontium chloride hexahydrate, 114 mg), RuCl3 (ruthenium chloride, 26 mg) and IrCl3 (iridium chloride, 5.3 mg) powder in 20 mL of ultrapure water, then add 1 g of ground cation exchange resin, adsorb at room temperature for 6 h, wash and dry after adsorption, and grind into powder;

[0188] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0189] (4) The heat-treated material was acid-washed with 20 mL of 2 mol / L hydrochloric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Sr. 0.5 Ru 0.4375 Ir 0.0625 O2; wherein, the water bath temperature is 40℃ and the water bath time is 8h.

[0190] Example 19: Sr 0.5 Ru 0.4375 Ir 0.0625 O2 catalyst

[0191] A catalyst Sr 0.5 Ru 0.4375 Ir 0.0625 O2, the preparation method of which includes the following steps:

[0192] (1) Clean the cation resin D001 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0193] (2) Dissolve the metal precursors SrCl2·6H2O (strontium chloride hexahydrate, 342 mg), RuCl3 (ruthenium chloride, 78 mg) and IrCl3 (iridium chloride, 15.9 mg) powder in 60 mL of ultrapure water, then add 5 g of ground cation exchange resin, adsorb at 80 °C for 2 h, wash and dry after adsorption, and grind into powder;

[0194] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 4 hours;

[0195] (4) The heat-treated material was acid-washed with 40 mL of 0.1 mol / L hydrochloric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Sr. 0.5 Ru 0.4375 Ir 0.0625 O2; wherein, the water bath temperature is 90℃ and the water bath time is 1h.

[0196] The catalyst Sr prepared above 0.5 Ru 0.4375 Ir 0.0625 O2, taking Example 17 as an example, its structural characterization diagram is shown below. Figure 7 ,in, Figure 7-1 For Sr 0.5 Ru 0.4375 Ir 0.0625 X-ray diffraction pattern of O2 Figure 7-2 For Sr 0.5 Ru 0.4375 Ir 0.0625 High-magnification transmission electron microscope image of O2. Figure 7-3 This represents the annular dark field and elemental energy spectrum. Figure 7-1 The XRD results showed results corresponding to the RuO2 standard card (PDF card), because the Sr doping did not change the crystal structure of RuO2. Figure 7-2 The results show that Sr 0.5 Ru 0.4375 Ir 0.0625 O2 is composed of nanocrystals of approximately 8 nm in size. Figure 7-3 The top left is the annular dark-field plot, showing Sr (top center), Ru (top right), Ir (bottom left), and O (bottom center). This indicates that Sr, Ru, Ir, and O are uniformly distributed in the sample.

[0197] Example 20: Ho 0.1 Nb0.1 Ru 0.7 Ir 0.1 O2 catalyst

[0198] A catalyst Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2, the preparation method of which includes the following steps:

[0199] (1) Clean the cation resin D254 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0200] (2) Dissolve the metal precursors HoCl3 (holmium chloride, 11 mg), C4H4NNbO9 (niobium ammonium oxalate, 11 mg), RuCl3 (ruthenium chloride, 52 mg) and IrCl3 (iridium chloride, 10.6 mg) powder in 50 mL of ultrapure water, then add 3 g of ground cation exchange resin, and adsorb at 40 °C for 4 h. After adsorption is complete, wash, dry and grind into powder.

[0201] (3) The product obtained in step (2) is directly heat-treated in air at 450°C for 6 hours;

[0202] (4) The heat-treated material was acid-washed with 40 mL of 1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Ho. 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2; wherein, the water bath temperature is 60℃ and the water bath time is 4h.

[0203] Example 21: Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2 catalyst

[0204] A catalyst Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2, the preparation method of which includes the following steps:

[0205] (1) Clean the cation resin D254 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0206] (2) Dissolve the metal precursors HoCl3 (holmium chloride, 5.5 mg), C4H4NNbO9 (niobium ammonium oxalate, 5.5 mg), RuCl3 (ruthenium chloride, 26 mg) and IrCl3 (iridium chloride, 5.2 mg) powder in 20 mL of ultrapure water, then add 1 g of ground cation exchange resin, adsorb at room temperature for 6 h, after adsorption is complete, wash and dry, and grind into powder;

[0207] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0208] (4) The heat-treated material was acid-washed with 10 mL of 2 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Ho. 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2; wherein, the water bath temperature is 40℃ and the water bath time is 8h.

[0209] Example 22: Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2 catalyst

[0210] A catalyst Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2, the preparation method of which includes the following steps:

[0211] (1) Clean the cation resin D254 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0212] (2) Dissolve the metal precursors HoCl3 (holmium chloride, 16.5 mg), C4H4NNbO9 (niobium ammonium oxalate, 16.5 mg), RuCl3 (ruthenium chloride, 78 mg) and IrCl3 (iridium chloride, 15.9 mg) powder in 60 mL of ultrapure water, then add 5 g of ground cation exchange resin, and adsorb at 80 °C for 2 h. After adsorption is complete, wash, dry and grind into powder.

[0213] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 4 hours;

[0214] (4) The heat-treated material was acid-washed with 40 mL of 0.1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Ho. 0.1 Nb 0.1Ru 0.7 Ir 0.1 O2; wherein, the water bath temperature is 90℃ and the water bath time is 1h.

[0215] The catalyst Ho prepared above 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2, taking Example 20 as an example, its structural characterization diagram is shown below. Figure 8 ,in, Figure 8-1 For Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 X-ray diffraction pattern of O2 Figure 8-2 For Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 High-magnification transmission electron microscope image of O2. Figure 8-3 This represents the annular dark field and elemental energy spectrum. Figure 8-1 The XRD results showed results corresponding to the RuO2 standard card (PDF card), indicating that the doping of Ho, Nb and Ir did not change the crystal structure of RuO2. Figure 8-2 The results showed that Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2 is composed of nanocrystals of approximately 7 nm in size. Figure 8-3 The top left of the image shows a ring-shaped dark field plot. Ho (top center), Nb (top right), Ru (bottom left), Ir (bottom center), and O (bottom right) indicate that the three elements Ho, Nb, Ru, Ir, and O are uniformly distributed in the sample.

[0216] Example 23: La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2 catalyst

[0217] A catalyst La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2, the preparation method of which includes the following steps:

[0218] (1) Clean the cation resin D61 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0219] (2) The metal precursors La(NO3)3·6H2O (lanthanum nitrate hexahydrate, 15.2 mg), Ce(NO3)3·6H2O (cerium nitrate hexahydrate, 15.2 mg), YCl3·6H2O (yttrium chloride hexahydrate, 10.6 mg), RuCl3 (ruthenium chloride, 104 mg) and IrCl3 (iridium chloride, 21.2 mg) powders were dissolved in 50 mL of ultrapure water, and then 3 g of ground cation exchange resin was added. The mixture was adsorbed at 30 °C for 6 h. After the adsorption was completed, the mixture was washed, dried and ground into powder.

[0220] (3) The product obtained in step (2) is directly heat-treated in air at 550°C for 10 hours;

[0221] (4) The heat-treated material was acid-washed with 40 mL of 1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain La. 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2; wherein, the water bath temperature is 50℃ and the water bath time is 2h.

[0222] Example 24: La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2 catalyst

[0223] A catalyst La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2, the preparation method of which includes the following steps:

[0224] (1) Clean the cation resin D61 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0225] (2) Dissolve the metal precursors La(NO3)3·6H2O (lanthanum nitrate hexahydrate, 7.6 mg), Ce(NO3)3·6H2O (cerium nitrate hexahydrate, 7.6 mg), YCl3·6H2O (yttrium chloride hexahydrate, 5.3 mg), RuCl3 (ruthenium chloride, 52 mg) and IrCl3 (iridium chloride, 10.6 mg) powder in 20 mL of ultrapure water, then add 1 g of ground cation exchange resin, and adsorb at room temperature for 6 h. After adsorption is complete, wash, dry and grind into powder.

[0226] (3) The product obtained in step (2) is directly heat-treated in air at 350°C for 12 hours;

[0227] (4) The heat-treated material was acid-washed with 10 mL of 2 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain La. 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2; wherein, the water bath temperature is 40℃ and the water bath time is 8h.

[0228] Example 25: La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2 catalyst

[0229] A catalyst La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2, the preparation method of which includes the following steps:

[0230] (1) Clean the cation resin D61 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0231] (2) Dissolve the metal precursors La(NO3)3·6H2O (lanthanum nitrate hexahydrate, 22.8 mg), Ce(NO3)3·6H2O (cerium nitrate hexahydrate, 22.8 mg), YCl3·6H2O (yttrium chloride hexahydrate, 15.9 mg), RuCl3 (ruthenium chloride, 156 mg) and IrCl3 (iridium chloride, 31.8 mg) powders in 60 mL of ultrapure water, then add 5 g of ground cation exchange resin, and adsorb at 80 °C for 2 h. After adsorption is complete, wash, dry and grind into powder.

[0232] (3) The product obtained in step (2) is directly heat-treated in air at 650°C for 4 hours;

[0233] (4) The heat-treated material was acid-washed with 40 mL of 0.1 mol / L nitric acid solution in a water bath, then washed until neutral, dried, and ground to obtain La. 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2; wherein, the water bath temperature is 90℃ and the water bath time is 1h.

[0234] The catalyst La prepared above 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2, taking Example 23 as an example, its structural characterization diagram is shown below. Figure 9 ,in, Figure 9-1 For La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 X-ray diffraction pattern of O2 Figure 9-2 For La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 High-magnification transmission electron microscope image of O2. Figure 9-3 This represents the annular dark field and elemental energy spectrum. Figure 9-1 The XRD results showed results corresponding to the RuO2 standard card (PDF card), indicating that the doping of La, Ce, Y and Ir did not change the crystal structure of RuO2. Figure 9-2 The results show that La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2 is composed of nanocrystals of approximately 7 nm in size. Figure 9-3 The top left of the image shows a ring-shaped dark field pattern. The numbers La (top left), Ce (top right), Y (top right), Ru (bottom left), Ir (bottom left), and O (bottom right) indicate that the three elements La, Ce, Y, Ru, Ir, and O are uniformly distributed in the sample.

[0235] Example 26: Sr 0.2 Ru 0.4 Ir 0.4 O2 catalyst

[0236] A catalyst Sr 0.2 Ru 0.4 Ir 0.4 O2, the preparation method of which includes the following steps:

[0237] (1) Clean the cation resin D85 with ultrapure water, let it air dry, and then grind it thoroughly in a grinder. Filter it through a 0.25mm (60 mesh) sieve and take the part smaller than 0.25mm (greater than 60 mesh) for later use.

[0238] (2) Dissolve the metal precursors SrCl2·6H2O (strontium chloride hexahydrate, 33.3 mg), RuCl3 (ruthenium chloride, 52 mg) and IrCl3 (iridium chloride, 74.2 mg) powder in 50 mL of ultrapure water, then add 3 g of ground cation exchange resin, and adsorb at 40 °C for 6 h. After adsorption is complete, wash, dry and grind into powder.

[0239] (3) The product obtained in step (2) is directly heat-treated in air at 450°C for 8 hours;

[0240] (4) The heat-treated material was acid-washed with 40 mL of 1 mol / L hydrochloric acid solution in a water bath, then washed until neutral, dried, and ground to obtain Sr. 0.2 Ru 0.4 Ir 0.4 O2; wherein, the water bath temperature is 60℃ and the water bath time is 2h.

[0241] The catalyst Sr prepared above 0.2 Ru 0.4 Ir 0.4 O2, its X-ray diffraction pattern is shown in Figure 10 .Depend on Figure 10 It can be known that Sr 0.2 Ru 0.4 Ir 0.4 The XRD results of O2 correspond to those of the RuO2 and IrO2 standard cards (PDF cards), indicating that Sr doping did not change the crystal structure of RuO2.

[0242] Experimental Example

[0243] 1. OER (electrocatalytic oxygen production) performance measurement

[0244] (1) Prepare a 0.1M perchloric acid (HClO4) solution as an electrolyte: Based on the concentration calculation, transfer 8 mL of perchloric acid (AR) into a 1L volumetric flask using a pipette and shake well;

[0245] (2) Preparation of catalyst ink: Take 4 mg of catalyst into a sample tube, add 1000 μL of isopropanol and 15 μL of Nafion (5 wt%) and ultrasonically disperse for 30 min;

[0246] (3) Preparation of catalyst-modified glass carbon electrode (GCE): 15 μL of the above catalyst ink was dropped onto a GCE with a diameter of 5 mm and allowed to dry naturally to form a catalyst film.

[0247] (4) Activity test: Using the catalyst-modified GCE as the working electrode, Ag / AgCl as the reference electrode, a high-purity stone rod as the counter electrode, and oxygen-saturated 0.1M HClO4 as the electrolyte solution, the activity was first activated for 50 cycles at a scan rate of 50 mV / s between potentials of 1.0 V and 1.5 V (relative to the standard hydrogen electrode (vs. RHE)) using cyclic voltammetry (CV); then, the potential-current curves were recorded at a scan rate of 5 mV / s between potentials of 1.0 V and 1.7 V using linear voltammetry (LSV) at a rotating disk speed of 1600 rpm.

[0248] (5) Data processing:

[0249] 1) Use the following formula to transform the x-coordinate: E = E c +E Ag / AgCl -IR

[0250] 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.

[0251] 2) Use the following formula to convert the modal coordinates J(mA / cm) 2 ) = I * 1000 / S

[0252] 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 .

[0253] 3) Calculate the OER overpotential

[0254] The OER activity map can be plotted using the data obtained from 1) and 2) above. The modal coordinate is set to 10 mA / cm². 2 The overpotential of the OER is the potential corresponding to the point where the water splitting theoretical potential of 1.23V is subtracted from the potential at ...

[0255] The OER performance test results are shown in […]. Figure 11-18 .

[0256] Depend on Figure 11 It can be known that Sr 0.2 Ru 0.4 Ir 0.4 10mA / cm of O2 2The overpotential at 1.8V was 211mV, while the overpotential of commercial RuO2 was 292mV. Commercial IrO2 did not even reach 10mA / cm at 1.8V. 2 This indicates that Sr 0.2 Ru 0.4 Ir 0.4 O2 has superior OER performance.

[0257] Depend on Figure 12 It can be seen that Pb2Ru2O 6.5 10mA / cm 2 The overpotential at the point is 174 mV, while the overpotential of commercial RuO2 is 292 mV, indicating that Pb2Ru2O 6.5 It has superior OER performance.

[0258] Depend on Figure 13 It can be seen that the catalyst RuO2 of the present invention has a strength of 10 mA / cm². 2 The overpotential at the point is 248mV, while the overpotential of commercial RuO2 is 292mV, indicating that the catalyst RuO2 of the present invention has superior OER performance.

[0259] Depend on Figure 14 It can be seen that the catalyst IrO2 of the present invention has a strength of 10 mA / cm². 2 The overpotential at this point is 308mV, while commercial IrO2 does not even reach 10mA / cm at 1.8V. 2 This indicates that the catalyst IrO2 of the present invention has superior OER performance.

[0260] Depend on Figure 15 It can be seen that the catalyst Ru of the present invention 0.7 Sn 0.3 10mA / cm of O2 2 The overpotential at the catalyst is 231 mV, while the overpotential of commercial RuO2 is 292 mV, indicating that the overpotential of the catalyst RuO2 in this invention is superior. 0.7 Sn 0.3 O2 has superior OER performance.

[0261] Depend on Figure 16 It can be known that Sr 0.5 Ru 0.4375 Ir 0.0.0625 10mA / cm of O2 2 The overpotential at 1.8V was 219mV, while the overpotential of commercial RuO2 was 292mV. Commercial IrO2 did not even reach 10mA / cm at 1.8V. 2 This indicates that Sr 0.5 Ru 0.4375 Ir 0.0.0625 O2 has superior OER performance.

[0262] Depend on Figure 17It can be seen that Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 10mA / cm of O2 2 The overpotential at 1.8V was 257mV, while the overpotential of commercial RuO2 was 292mV, and commercial IrO2 did not even reach 10mA / cm. 2 This indicates Ho 0.1 Nb 0.1 Ru 0.7 Ir 0.1 O2 has superior OER performance.

[0263] Depend on Figure 18 It can be seen that La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 10mA / cm of O2 2 The overpotential at 1.8V was 220mV, while the overpotential of commercial RuO2 was 292mV, and commercial IrO2 did not even reach 10mA / cm. 2 This indicates that La 0.05 Ce 0.05 Y 0.1 Ru 0.7 Ir 0.1 O2 has superior OER performance.

[0264] 2. ORR performance measurement

[0265] (1) Prepare a 0.1M perchloric acid (HClO4) solution as an electrolyte: Based on the concentration calculation, transfer 8mL of perchloric acid (AR) into a 1L volumetric flask through a pipette, make up to volume, and shake well;

[0266] (2) Preparation of catalyst ink: Take 4 mg of catalyst into a sample tube, add 1000 μL of isopropanol and 15 μL of Nafion (5 wt%) and ultrasonically disperse for 30 min.

[0267] (3) Preparation of catalyst-modified glass carbon electrode (GCE): 3.5 μg of Pt (the volume of the catalyst ink is measured according to the Pt loading of the catalyst) is drop-coated onto a GCE with a diameter of 5 mm and allowed to dry naturally to form a catalyst film.

[0268] (4) Activity test: Using the catalyst-modified GCE as the working electrode, Ag / AgCl as the reference electrode, a high-purity stone rod as the counter electrode, and oxygen-saturated 0.1M HClO4 as the electrolyte solution, the activity was first activated for 50 cycles at a scan rate of 50 mV / s between potentials of 0 V and 1.2 V (relative to the standard hydrogen electrode (vs. RHE)) using cyclic voltammetry (CV); then, using linear voltammetry (LSV) at a rotating disk speed of 1600 rpm, the potential was scanned from 1.1 V to 0 V and then from 0 V to 1.1 V, and the potential-current curves were recorded.

[0269] (5) Data processing: Only the curve from 0V to 1.1V is taken and the following data processing is performed.

[0270] 1) Use the following formula to transform the x-coordinate: E = E c +E Ag / AgCl -IR

[0271] 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.

[0272] 2) Use the following formula to convert the modal coordinates J(mA / cm) 2 ) = I * 1000 / S

[0273] 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 .

[0274] The ORR performance measurement results are shown in [link to data]. Figure 19 . Figure 19 The results show that Pt loading on Ru 0.7 Ti 0.3 The O2 carrier exhibited an ORR half-wave potential of 0.875V, while Pt / C showed 0.859V, indicating that the Pt loading on Ru... 0.7 Ti 0.3 The O2 vector exhibits better ORR activity.

[0275] 3. Stability Test

[0276] (1) After testing the activity using the above method, maintain a constant potential of 1.5V for 3h in oxygen-saturated 0.1M HClO4.

[0277] (2) Activate again using cyclic voltammetry (CV) at a scan rate of 50 mV / s between potentials of 0 V and 1.2 V (relative to the standard hydrogen electrode (vs. RHE)) for 50 cycles.

[0278] (3) The ORR activity was tested again using LSV (the same method as the above activity test).

[0279] The results of the stability performance test are shown in Figure 20 and Figure 21 . Figure 20 Pt / Ru 0.7 Ti 0.3 The ORR polarization curve of the O2 catalyst after constant voltage aging at 1.5V for 3 hours was almost identical to that before aging, indicating that the Pt / Ru catalyst... 0.7 Ti 0.3 O2 has good antioxidant properties. Figure 21 The ORR polarization curve of the Pt / C catalyst after constant voltage aging at 1.5V for 3 hours differed by 47 mV from that before aging, indicating that the ORR performance of the Pt / C catalyst deteriorated after oxidation. Combining these two results, it is evident that oxide supports exhibit better oxidation resistance and stability compared to carbon supports.

[0280] 4. Fuel cell anode anti-reverse polarity performance test

[0281] (1) Preparation of anode catalyst ink: Weigh 1.04 mg of 60 wt% Pt / C (Pt accounts for 60 wt% by mass) and 0.1 mg of Pb2Ru2O 6.5 As for the sample tube, add 800uL of isopropanol and 5.7uL of Nafion, and disperse them evenly by ultrasonication.

[0282] (2) Preparation of anode catalyst ink: Weigh 2.13 mg of 60 wt% Pt / C (Pt mass accounts for 60 wt%) into a sample tube, add 800 uL of isopropanol and 11.4 uL of Nafion, and disperse evenly by ultrasonication.

[0283] (3) MEA preparation: The above-mentioned catalyst ink was sprayed onto both sides of the hp membrane (a type of proton exchange membrane), with a spraying area of ​​2.5*2.5cm. 2 This results in a Pt loading of 0.1 mg / cm³ at the anode. 2 The cathode Pt loading is 0.2 mg / cm³. 2The area of ​​the sprayed catalyst was sandwiched between the anode and cathode with 2.5cm*2.5cm carbon paper as a gas diffusion layer. The MEA electrode was prepared by hot pressing for 3 minutes under the conditions of 50MPa pressure and 135 degrees Celsius.

[0284] (4) Reverse electrode performance test: The above-mentioned MEA electrode was assembled in the fuel cell, and the conditions of the fuel electrode were set as follows: pure H2 was introduced through the anode, humidified to 100%, temperature 80 degrees Celsius, and pressure 100 kPa; dry air was introduced through the cathode, humidified to 100%, temperature 80 degrees Celsius, and pressure 100 kPa. The cell was first activated to a stable state between 0.2 V and 0.9 V, and then the battery activity was tested again. The H2 introduced through the anode was changed to N2, and an external electrochemical workstation was used to connect the working electrode to the anode of the fuel cell, and the counter electrode and reference electrode to the cathode of the fuel cell. Constant current electrolysis (1.25 A, 0.2 A / cm²) was then performed. 2 10 min. After electrolysis is complete, H2 is reintroduced into the anode and activated until stable before testing the battery activity again.

[0285] (5) The preparation and testing methods without Pb2Ru2O6.5 are the same as those described above.

[0286] The results of the reverse polarity performance test are shown below. Figure 22 and Figure 23 . Figure 22 The study showed the performance comparison of the Pt / C catalyst before and after the reverse electrode. The peak power of Pt / C before the reverse electrode was 554 mW, and after the reverse electrode it was 400 mW. The results indicate that the peak power of Pt / C after the reverse electrode decreased by 27.6%. Figure 23 This indicates that the Pt / C catalyst, when mixed with Pb₂Ru₂O, [is effective]. 6.5 After the catalyst, although the peak power (506 mW) decreased slightly compared to Pt / C, the peak power after the reverse electrode (480 mW) only decreased by 5.0%. This indicates that the addition of Pb₂Ru₂O... 6.5 Catalysts can improve the resistance to reverse polarity.

[0287] 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 catalyst, characterized in that, Includes the following steps: (1) Dissolve the soluble metal precursor salt in water, then add cation exchange resin for adsorption, and after adsorption, wash, dry and grind; the metal is at least one of Ru, Ir, Pb, Ti, Y, Sn, Sr, Ta, Sb, La, Zr, Mo, Nb, Ho and Ce. (2) The product obtained in step (1) is directly heat-treated in air at a temperature of 350-650℃ for 4-12 hours. The heat-treated product is then acid-washed, water-washed, dried, and ground to obtain the final product. The above preparation method also includes: mixing the product obtained in step (2) with a noble metal salt solution, letting it stand, and then annealing it to obtain a supported catalyst; the temperature during the standing process is room temperature to 80°C, and the standing time is 12-24h; the annealing temperature is 200-500°C, and the annealing time is 3-10h.

2. The method for preparing the catalyst according to claim 1, characterized in that, It also includes a pretreatment process for the cation exchange resin, specifically: the cation exchange resin is ground through a 60-mesh sieve, and the portion larger than 60 mesh is the pretreated cation exchange resin.

3. The method for preparing the catalyst according to claim 1, characterized in that, In step (1), the weight ratio of cation exchange resin to water is 1-5:20-60.

4. The method for preparing the catalyst according to claim 1, characterized in that, In step (1), the adsorption temperature is room temperature - 80℃ and the adsorption time is 2-6h.

5. The method for preparing the catalyst according to claim 1, characterized in that, In step (2), the pickling temperature is 40-90℃ and the pickling time is 1-8h.

6. The method for preparing the catalyst according to claim 1, characterized in that, The mass ratio of the product obtained in step (2) to the precious metal in the precious metal salt solution is 1:19-6:

4.

7. The method for preparing the catalyst according to claim 1, characterized in that, The catalyst is Pt / Ru. x Ti 1-x O2, where 0 < x < 1.

8. The application of the catalyst prepared by any one of claims 1-7 as a catalyst support for the cathode oxygen reduction reaction in fuel cells.

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