Strong-acid-corrosion-resistant carbon-loaded platinoid all-alloy nano material and preparation method thereof

Abstract

The invention discloses a strong-acid-corrosion-resistant carbon-loaded platinoid all-alloy nano material and a preparation method thereof, and relates to the technical field of new energy materials. The preparation method of the carbon-loaded platinoid all-alloy nano material comprises the following steps: dispersing a carbon carrier in a solvent, adding platinum and copper precursors, dispersing, and adsorbing at constant temperature to obtain a suspension mixed solution; drying by distillation, drying and grinding to obtain a solid compound; calcining in an inert atmosphere, and cooling to obtain a carbon-supported platinoid material; and carrying out strong acid corrosion treatment, washing, drying and grinding to obtain the strong acid corrosion resistant carbon-loaded platinoid all-alloy nano material. The prepared material can keep the crystal structure stable in a strong acid environment and has excellent acid corrosion resistance, and the platinum-copper nano material takes platinum as a solvent and copper as a solute to form a complete alloy phase with the atomic ratio of copper to platinum being greater than or equal to 1: 1. When the material is used as an oxygen reduction catalyst, the atom utilization rate of platinum is high, and meanwhile, the oxygen reduction reaction catalytic activity and long-term stability of the material are remarkably improved.

Description

Technical Field

[0001] This invention relates to a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion and its preparation method, belonging to the field of new energy materials technology. Background Technology

[0002] Proton exchange membrane fuel cells (PEMFCs) typically use platinum-based catalysts as both anode and cathode materials. The oxygen reduction reaction (ORR) at the cathode is much slower than the hydrogen oxidation reaction (HOR) at the anode, thus requiring more platinum to promote the cathode reaction. However, platinum resources are scarce and expensive, resulting in high costs for platinum-based catalysts. Overcoming this cost bottleneck is crucial for the large-scale commercialization of PEMFCs.

[0003] Alloying platinum (Pt) with inexpensive transition metals (M, such as Fe, Co, Cu, Ni) to prepare PtM alloy catalysts is an effective strategy to improve performance and reduce platinum usage. Introducing transition metals with smaller atomic radii induces a lattice compression effect, shortening Pt-Pt bond lengths and weakening the adsorption of oxygen-containing intermediates at catalytic sites. Simultaneously, electronic interactions optimize the electronic configuration of the platinum surface, reducing the d-band center of platinum atoms and lowering the adsorption energy of oxygen species, thereby significantly improving ORR activity. Related techniques show that in platinum-copper alloys, each platinum atom is coordinated by multiple copper atoms. This synergistic regulation of geometry and electronic structure not only optimizes the adsorption energy of oxygen intermediates at platinum active sites but also significantly reduces the reaction energy barrier. Compared to pure platinum catalysts, platinum-copper alloys can reduce platinum usage while maintaining or even improving ORR activity, thus demonstrating potential for low-cost applications in proton exchange membrane fuel cells and other energy conversion devices.

[0004] Proton exchange membrane fuel cells operate in an acidic environment, meaning their catalysts must possess both high activity and high durability under acidic conditions. However, most current alloy catalysts are prone to transition metal dissolution under long-term acidic conditions, leading to structural collapse, aggregation, or stripping of catalyst nanoparticles from the carbon support, thus significantly reducing the number of platinum active sites. More seriously, the dissolved metal ions may further contaminate the entire battery system, even causing short circuits and complete failure. Therefore, developing a method to prepare highly alloyed catalysts resistant to strong acid corrosion is of significant and urgent practical importance for improving the stability of cathode catalysts in acidic environments and suppressing transition metal ion dissolution. Summary of the Invention

[0005] To address the shortcomings of related technologies, this invention provides a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion and its preparation method. The material prepared by this invention has the advantages of improving the stability of the cathode catalyst in an acidic environment and inhibiting the dissolution of transition metal ions, thus solving the problem of transition metal dissolution in alloy catalysts.

[0006] One objective of this invention is to provide a method for preparing carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion, specifically including the following steps: (1) The carbon support is dispersed in a solvent to form a dispersion, and then the platinum precursor and copper precursor are added to the dispersion and dispersed. Then, the constant temperature adsorption treatment is carried out to obtain a suspension mixture.

[0007] (2) The suspension mixture was evaporated to dryness to obtain a mixture containing platinum precursor, copper precursor and carbon support. The mixture was dried and ground to obtain a solid composite.

[0008] (3) The solid composite was calcined in an inert atmosphere and then cooled to obtain carbon-supported platinum-copper material.

[0009] (4) The carbon-supported platinum-copper material is placed in a strong acid solution for strong acid corrosion resistance treatment to obtain the carbon-supported platinum-copper material after strong acid corrosion resistance treatment. The carbon-supported platinum-copper material after strong acid corrosion resistance treatment is washed, dried and ground to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0010] Preferably, the solvent in step (1) is anhydrous ethanol; the amount of carbon support added in the dispersion is 2~6 mg / mL.

[0011] Preferably, the carbon support in step (1) is one of Ketjen Black EC-300J, Ketjen Black EC-600J, Cabot BP2000 or Cabot XC-72.

[0012] More preferably, the carbon support in step (1) is one of Cabot BP2000 and Ketjen Black EC300J.

[0013] Preferably, in step (1), the platinum precursor is one of chloroplatinic acid, platinum acetylacetonate, platinum chloride, platinum nitrate, ethanolamine hydroxyplatinum, and dihydroxytetramineplatinum; and the copper precursor is one of copper acetylacetonate, copper chloride, copper nitrate, and copper sulfate.

[0014] More preferably, the copper precursor in step (1) is one of copper acetylacetonate or copper nitrate.

[0015] Preferably, in step (1), the platinum precursor is added to the dispersion at a mass ratio of carbon support to platinum precursor of 1:(1~4); in step (1), the copper precursor is added to the dispersion at a mass ratio of carbon support to copper precursor of 1:(2~6).

[0016] Preferably, the conditions for the isothermal adsorption treatment in step (1) are: isothermal adsorption at 60~80℃ for 18~30h.

[0017] More preferably, the isothermal adsorption treatment in step (1) is carried out under stirring.

[0018] Preferably, the inert atmosphere in step (3) is nitrogen or argon; the calcination conditions are: heating to 800-1100°C at a heating rate of 1-50°C / min, and holding for 3-10 hours.

[0019] More preferably, the inert atmosphere in step (3) is high-purity nitrogen or argon.

[0020] More preferably, the heating rate of the calcination in step (3) is 10~30℃ / min.

[0021] Preferably, the strong acid solution in step (4) is one or more of acetic acid, sulfuric acid or nitric acid aqueous solution; the concentration of the strong acid solution is 5~10 mol / L; the temperature of the strong acid solution is 60~90℃; and the time of the strong acid corrosion resistance treatment is 10~18h.

[0022] The second objective of this invention is to provide a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion, prepared using the method of this invention.

[0023] Mechanism of the invention: This invention achieves simultaneous reduction and full alloying of platinum-copper bimetallic precursors through the synergistic effect of a high-temperature-induced thermal reduction process and high-concentration acid corrosion treatment. It also removes unalloyed platinum-copper and structurally unstable alloys from the material, retaining only the fully alloyed platinum-copper alloy, thus improving the material's stability and platinum atom utilization in subsequent catalytic reactions. This invention relates to a method for preparing highly acid-resistant carbon-supported platinum-copper full alloy nanomaterials, the mechanism of which is as follows: (1) Under an inert atmosphere, this invention utilizes a high-temperature-induced thermal reduction process to directly and simultaneously reduce platinum and copper bimetallic precursors to a metallic state without relying on external reducing agents or reducing gases, and drives them to undergo atomic-level interdiffusion and fusion on the carbon support surface. This process not only achieves efficient reduction of the metal precursors, but also constructs a platinum-copper all-alloy phase structure dominated by a high degree of alloying in situ on the carbon support, providing a material basis with differentiated stability for subsequent selective corrosion.

[0024] (2) Based on the differences in alloying degree caused by the above-mentioned thermal reduction process, the present invention further introduces strong acid corrosion treatment. In this process, the platinum-copper components that are not fully alloyed in the high-temperature reduction stage or the copper phase with low alloying degree have poor structural stability and preferentially react with acid to form soluble salts and are dissolved and removed; the platinum-copper phase with a highly alloyed structure formed by high temperature induction has excellent acid corrosion resistance due to the strong interatomic interaction and is thus completely preserved. Through the synergistic effect of the high-temperature thermal reduction process and the high-concentration acid corrosion treatment, the material prepared by the present invention retains only fully alloyed platinum-copper nanocrystals with consistent structure and stable composition.

[0025] (3) The carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion prepared by this invention has a complete alloy crystal structure, high metal loading and clean alloy surface under the synergistic effect of alloying and strong acid corrosion treatment. It exhibits significantly enhanced catalytic activity and long-term stability in oxygen reduction reaction. The improved acid corrosion resistance further ensures the structural durability and performance retention rate under acidic working conditions.

[0026] The beneficial effects of this invention are: (1) This invention provides a green preparation process for carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion. This process uses only carbon support and platinum-copper precursors as raw materials, without adding external reducing agents, and can achieve in-situ synthesis and loading of active components through simple steps. The total mass percentage of platinum and copper in the prepared carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion is ≥50% of the total mass of the material; the platinum-copper nanomaterials use platinum as solvent and copper as solute, forming a complete alloy phase structure with a copper-platinum atomic ratio ≥1:1, as well as strong acid corrosion resistance and excellent oxygen reduction reaction catalytic performance; the crystal structure of the carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion prepared by this invention is consistent before and after strong acid corrosion treatment; this method significantly shortens the catalyst preparation process, avoids the generation of reducing agent-related waste from the source, makes the process easier to scale up for production, and has high batch-to-batch consistency, which is in line with the principles of green chemistry.

[0027] (2) The synergistic effect of the high-temperature thermal reduction and strong acid corrosion process in this invention can efficiently remove free copper and low-alloyed components that have failed to form a stable alloy phase with platinum, while completely preserving the platinum-copper full alloy phase with excellent acid corrosion resistance. This process not only significantly improves the structural uniformity and chemical stability of the active phase in the catalyst, but also obtains carbon-supported platinum-copper full alloy nanomaterials that maintain high durability in a strong acid environment, greatly enhancing their oxygen reduction reaction performance and long-term stability under harsh conditions.

[0028] (3) The high metal loading platinum-copper all-alloy nanomaterial catalyst prepared by the present invention achieves efficient substitution of platinum atoms by copper and all-alloy structure, which significantly reduces the amount of precious metal platinum while maintaining high performance and greatly saves material costs; the all-alloy characteristics synergistically improve the metal loading, improve the utilization rate of platinum atoms, and enhance intrinsic catalytic activity; at the same time, the material can maintain the total metal loading unchanged under the condition of reducing the thickness of the cathode catalyst layer, thereby effectively shortening the transport path of protons and oxygen, alleviating the mass transfer limitation and voltage loss problem under high current density, and providing a key material basis for the development of high-performance, long-life fuel cells and other related electrochemical devices. Attached Figure Description

[0029] Figure 1 The images show the X-ray diffraction (XRD) patterns of the carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion prepared in Examples 1-3 and Comparative Examples 1-2 of this invention.

[0030] Figure 2 This is a TEM image of the carbon-supported platinum-copper alloy nanomaterial resistant to strong acid corrosion prepared in Example 2 of the present invention.

[0031] Figure 3 This is a high-resolution TEM image of the carbon-supported platinum-copper alloy nanomaterial resistant to strong acid corrosion prepared in Example 2 of this invention.

[0032] Figure 4 The high-resolution X-ray photoelectron spectroscopy (XPS) spectra of the strong acid-resistant carbon-supported platinum-copper alloy nanomaterial Pt4f prepared in Examples 1-3 of this invention are shown.

[0033] Figure 5 The images show the Cu 2p XPS fine scan spectra of the carbon-supported platinum-copper alloy nanomaterials resistant to strong acid corrosion prepared in Examples 1-3 of this invention.

[0034] Figure 6 Cyclic voltammetry (CV) curves of the acid-resistant carbon-supported platinum-copper alloy nanomaterials prepared in Examples 2 and 4 of this invention in a N2-saturated 0.1 M HClO4 solution.

[0035] Figure 7 The polarization (LSV) curves of the strong acid corrosion resistant carbon-supported platinum-copper alloy nanomaterials prepared in Examples 2 and 4 of this invention in O2-saturated 0.1 M HClO4 solution are shown.

[0036] Figure 8 The cyclic voltammetry (CV) diagrams of the materials prepared in Example 2 and Comparative Example 1 of this invention in a 0.1 M HClO4 solution saturated with N2 are shown.

[0037] Figure 9The polarization (LSV) diagrams of the materials prepared in Example 2 and Comparative Example 1 of this invention in an O2-saturated 0.1 M HClO4 solution are shown.

[0038] Figure 10 The CV diagrams are for the materials prepared in Example 2 and Comparative Example 2 of this invention in a 0.1 M HClO4 solution saturated with N2.

[0039] Figure 11 The LSV diagrams are for the materials prepared in Example 2 and Comparative Example 2 of this invention in an O2-saturated 0.1 M HClO4 solution.

[0040] Figure 12 The bar chart shows the comparison of the electrochemical active area (ECSA) of the material prepared in Example 2 of this invention after 10,000, 20,000, and 30,000 CV cycles (0.6~0.95V) in a N2-saturated 0.1 M HClO4 solution with the initial value.

[0041] Figure 13 The bar chart shows the comparison of the mass activity (MA) of the material prepared in Example 2 of this invention after 10,000, 20,000, and 30,000 CV cycles (0.6~0.95V) in a N2-saturated 0.1 M HClO4 solution with the initial value. Detailed Implementation

[0042] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments. In the embodiments and comparative examples of this invention, unless otherwise specified, all chemical reagents used were commercially available analytical grade reagents.

[0043] Example 1 A method for preparing a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion (the metal loading of the carbon-supported platinum-copper all-alloy nanomaterial is 64.72% by mass percentage) specifically includes the following steps: (1) Carbon carrier Cabot BP2000 was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Cabot BP2000 added to the dispersion was 3.33 mg / mL. Then, platinum precursor (platinum acetylacetonate) and copper precursor (copper nitrate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 60℃ and magnetic stirring at 500 rpm for 24 h in a constant temperature water bath to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of carbon carrier to platinum precursor of 1:1.5, and the copper precursor was added to the dispersion at a mass ratio of carbon carrier to copper precursor of 1:2.5.

[0044] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0045] (3) The solid composite was placed in a tube furnace and calcined at 900°C for 3 hours at a heating rate of 5°C / min under a high-purity nitrogen atmosphere to reduce the platinum copper and fully alloy it. Then the furnace was cooled to room temperature to obtain a black solid powder, namely carbon-supported platinum copper material.

[0046] (4) The carbon-supported platinum-copper material was placed in a 5 mol / L, 80℃ aqueous acetic acid solution for 16 h to undergo strong acid corrosion treatment to obtain the carbon-supported platinum-copper material after strong acid corrosion treatment. The carbon-supported platinum-copper material after strong acid corrosion treatment was washed with an aqueous ethanol solution (the aqueous ethanol solution was prepared by mixing deionized water and anhydrous ethanol with a purity ≥99.7% in a volume ratio of 4:1) until neutral. Then it was dried at 60℃ and vacuum degree ≤0.08MPa for 8 h and then ground into a uniform powder to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0047] Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to quantitatively analyze the metal elements of the carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion prepared in this embodiment. The platinum loading was found to be 33.01% by mass, the copper loading was 31.71% by mass, and the total metal loading was 64.72% by mass. Based on this, the platinum-copper atomic ratio was calculated to be approximately 1:2.95.

[0048] The fine scanned spectrum of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterials prepared in this embodiment ( Figure 4 , Figure 5 The results show that the Pt 4f peak in Example 1 exhibits a negative shift compared to the 71.7 eV of Pt in Pt / C, and the Cu 2p peak shows a positive shift compared to the Cu 2p binding energy of 932.7 eV measured on pure Cu, indicating that low electronegativity Cu atoms have entered the Pt lattice in Example 1. The ORR catalytic performance of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial prepared in Example 1 was tested, and the electrochemical area of ​​the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial in Example 1 was found to be 10² m². 2 / g, with a mass activity of 753mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 30%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 36%.

[0049] Example 2 A method for preparing a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion (the metal loading of the carbon-supported platinum-copper all-alloy nanomaterial is 71.82% by mass percentage) specifically includes the following steps: (1) Carbon carrier Cabot BP2000 was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Cabot BP2000 added to the dispersion was 3.33 mg / mL. Then, platinum precursor (platinum acetylacetonate) and copper precursor (copper nitrate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 60℃ and magnetic stirring at 500 rpm for 24 h in a constant temperature water bath to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of carbon carrier to platinum precursor of 1:2, and the copper precursor was added to the dispersion at a mass ratio of carbon carrier to copper precursor of 1:5.

[0050] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0051] (3) The solid composite was placed in a tube furnace and calcined at 900°C for 3 hours at a heating rate of 5°C / min under a high-purity argon atmosphere to reduce the platinum copper and fully alloy it. Then, it was cooled to room temperature with the furnace to obtain a black solid powder, namely carbon-supported platinum copper material.

[0052] (4) The carbon-supported platinum-copper material was placed in a 6 mol / L sulfuric acid aqueous solution at 90°C for 16 h to undergo strong acid corrosion treatment to obtain the carbon-supported platinum-copper material after strong acid corrosion treatment. The carbon-supported platinum-copper material after strong acid corrosion treatment was washed with an aqueous solution of ethanol (the aqueous solution of ethanol was prepared by mixing deionized water and anhydrous ethanol with a purity ≥99.7% in a volume ratio of 4:1) until neutral. Then it was dried at 60°C and vacuum degree ≤0.08MPa for 8 h and then ground into a uniform powder to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0053] The metal element content of the material prepared in this embodiment was quantitatively analyzed by ICP. The results showed that the platinum loading was 36.38% by mass, the copper loading was 35.44% by mass, and the total metal loading was 71.82% by mass. Based on this, the platinum-copper atomic ratio was calculated to be approximately 1:2.99.

[0054] From TEM ( Figure 2 , Figure 3As can be seen, nanoparticles with an average size of approximately 8.03 nm are uniformly dispersed on the surface of the carbon support, and the interatomic spacing of the PtCu3 alloy (111) crystal plane is 0.213 nm. This indicates that the present invention can achieve the deposition of uniformly dispersed PtCu nanoparticles on the surface of a conductive carbon support. XPS fine scan spectrum of carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion ( Figure 4 , Figure 5 The results show that the Pt 4f peak in Example 2 is negatively shifted compared to the 71.7 eV of Pt in Pt / C, indicating that the binding energy of Pt is reduced in Example 2. The Cu 2p peak in Example 2 is left-shifted compared to the Cu 2p binding energy of 932.7 eV measured on pure Cu, indicating that there is a strong electronic interaction between Pt and Cu, with electrons transferring from Cu (low electronegativity) to Pt (high electronegativity), which modulates the adsorption energy of oxygen-containing intermediates on the surface, thereby improving the catalytic activity of the material.

[0055] The ORR catalytic performance of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial prepared in Example 2 was tested. The test results showed that the electrochemical area of ​​the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial in Example 2 was 61 m². 2 / g, with a mass activity of 866mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 17.8%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 19%.

[0056] Example 3 A method for preparing a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion (the metal loading of the carbon-supported platinum-copper all-alloy nanomaterial is 74.15% by mass percentage) specifically includes the following steps: (1) Carbon carrier Cabot BP2000 was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Cabot BP2000 added to the dispersion was 3.33 mg / mL. Then, platinum precursor (platinum acetylacetonate) and copper precursor (copper nitrate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 60℃ and magnetic stirring at 500 rpm for 24 h in a constant temperature water bath to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of carbon carrier to platinum precursor of 1:3, and the copper precursor was added to the dispersion at a mass ratio of carbon carrier to copper precursor of 1:6.

[0057] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0058] (3) The solid composite was placed in a tube furnace and calcined at 900°C for 3 hours at a heating rate of 5°C / min under a high-purity nitrogen atmosphere to reduce the platinum copper and fully alloy it. Then the furnace was cooled to room temperature to obtain a black solid powder, namely carbon-supported platinum copper material.

[0059] (4) The carbon-supported platinum-copper material was placed in an 8 mol / L, 90℃ nitric acid aqueous solution for 16 h to undergo strong acid corrosion treatment to obtain the carbon-supported platinum-copper material after strong acid corrosion treatment. The carbon-supported platinum-copper material after strong acid corrosion treatment was washed with an aqueous solution of ethanol (the aqueous solution of ethanol was prepared by mixing deionized water and anhydrous ethanol with a purity ≥99.7% in a volume ratio of 4:1) until neutral. Then it was dried at 60℃ and vacuum degree ≤0.08MPa for 8 h and then ground into a uniform powder to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0060] The metal element content of the material prepared in this embodiment was quantitatively analyzed by ICP. The results showed that the platinum loading was 36.07% by mass, the copper loading was 38.08% by mass, and the total metal loading was 74.15% by mass. Based on this, the platinum-copper atomic ratio was calculated to be approximately 1:3.24.

[0061] XPS fine scan spectrum ( Figure 4 , Figure 5 The results showed that the Pt 4f peak in Example 3 exhibited a negative shift compared to the 71.7 eV of Pt in Pt / C, and the Cu 2p peak showed a positive shift compared to the Cu 2p binding energy of 932.7 eV measured on pure Cu, indicating that low electronegativity Cu atoms entered the Pt lattice in Example 3. The ORR catalytic performance of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial prepared in Example 3 was tested, and the electrochemical area of ​​the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial in Example 3 was found to be 79 m². 2 / g, with a mass activity of 670mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 33%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 37%.

[0062] Example 4 A method for preparing a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion (the metal loading of the carbon-supported platinum-copper all-alloy nanomaterial is 71.56% by mass percentage) specifically includes the following steps: (1) The carbon support Ketjen Black EC300J was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Ketjen Black EC300J added to the dispersion was 3.33 mg / mL. Then, the platinum precursor (platinum acetylacetonate) and the copper precursor (copper nitrate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 60℃ and magnetic stirring at 500 rpm for 24 h in a constant temperature water bath to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of carbon support to platinum precursor of 1:2, and the copper precursor was added to the dispersion at a mass ratio of carbon support to copper precursor of 1:5.

[0063] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0064] (3) The solid composite was placed in a tube furnace and calcined at 900°C for 3 hours at a heating rate of 5°C / min under a high-purity nitrogen atmosphere to reduce the platinum copper and fully alloy it. Then the furnace was cooled to room temperature to obtain a black solid powder, namely carbon-supported platinum copper material.

[0065] (4) The carbon-supported platinum-copper material was placed in a 10 mol / L, 90°C acetic acid aqueous solution and subjected to strong acid corrosion treatment for 16 h to obtain the carbon-supported platinum-copper material after strong acid corrosion treatment. The carbon-supported platinum-copper material after strong acid corrosion treatment was washed with an aqueous solution of ethanol (the aqueous solution of ethanol was prepared by mixing deionized water and anhydrous ethanol with a purity ≥99.7% in a volume ratio of 4:1) until neutral. Then it was dried at 60°C and vacuum degree ≤0.08MPa for 8 h and then ground into a uniform powder to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0066] ICP was used to quantitatively analyze the metal element content of the material prepared in this example. The results showed that the platinum loading was 35.72% by mass, the copper loading was 35.84% by mass, and the total metal loading was 71.56% by mass. Based on this, the platinum-copper atomic ratio was calculated to be approximately 1:3.08. The ORR catalytic performance of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial prepared in Example 4 was tested. The test results showed that the electrochemical area of ​​the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial in Example 4 was 80 m². 2 / g, with a mass activity of 564mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 38%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 42%.

[0067] Example 5 A method for preparing a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion (the metal loading of the carbon-supported platinum-copper all-alloy nanomaterial is 62.60% by mass percentage) specifically includes the following steps: (1) The carbon support Ketjen Black EC300J was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Ketjen Black EC300J added to the dispersion was 2 mg / mL. Then, the platinum precursor (platinum chloride) and the copper precursor (copper acetylacetonate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 70°C and magnetic stirring at 500 rpm for 18 h to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of 1:1 between the carbon support and the platinum precursor, and the copper precursor was added to the dispersion at a mass ratio of 1:2 between the carbon support and the copper precursor.

[0068] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0069] (3) The solid composite was placed in a tube furnace and calcined at 800°C for 10 hours under a high-purity nitrogen atmosphere at a heating rate of 10°C / min to reduce the platinum copper and fully alloy it. Then, it was cooled to room temperature with the furnace to obtain a black solid powder, namely carbon-supported platinum copper material.

[0070] (4) The carbon-supported platinum-copper material was placed in a 10 mol / L, 60°C acetic acid aqueous solution and subjected to strong acid corrosion treatment for 18 h to obtain the carbon-supported platinum-copper material after strong acid corrosion treatment. The carbon-supported platinum-copper material after strong acid corrosion treatment was washed with an aqueous solution of ethanol (the aqueous solution of ethanol was prepared by mixing deionized water and anhydrous ethanol with a purity ≥99.7% in a volume ratio of 4:1) until neutral. Then it was dried at 60°C and vacuum degree ≤0.08MPa for 8 h and then ground into a uniform powder to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0071] ICP was used to quantitatively analyze the metal element content of the material prepared in this example. The results showed that the platinum loading was 31.88% by mass, the copper loading was 30.72% by mass, and the total metal loading was 62.60% by mass. Based on this, the platinum-copper atomic ratio was calculated to be approximately 1:2.96. The ORR catalytic performance of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial prepared in Example 5 was tested. The test results showed that the electrochemical area of ​​the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial in Example 5 was 53 m². 2 / g, with a mass activity of 571mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 34%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 37%.

[0072] Example 6 A method for preparing a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion (the metal loading of the carbon-supported platinum-copper all-alloy nanomaterial is 78.08% by mass percentage) specifically includes the following steps: (1) The carbon support Ketjen Black EC300J was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Ketjen Black EC300J added to the dispersion was 6 mg / mL. Then, the platinum precursor (chloroplatinic acid) and the copper precursor (copper acetylacetonate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 80℃ and magnetic stirring at 500 rpm for 30 h in a constant temperature water bath to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of carbon support to platinum precursor of 1:4, and the copper precursor was added to the dispersion at a mass ratio of carbon support to copper precursor of 1:6.

[0073] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0074] (3) The solid composite was placed in a tube furnace and calcined at 1100°C for 4 hours under a high-purity nitrogen atmosphere at a heating rate of 30°C / min to reduce the platinum copper and fully alloy it. Then, it was cooled to room temperature with the furnace to obtain a black solid powder, namely carbon-supported platinum copper material.

[0075] (4) The carbon-supported platinum-copper material was placed in a 10 mol / L, 70°C acetic acid aqueous solution and subjected to strong acid corrosion treatment for 10 h to obtain the carbon-supported platinum-copper material after strong acid corrosion treatment. The carbon-supported platinum-copper material after strong acid corrosion treatment was washed with an aqueous solution of ethanol (the aqueous solution of ethanol was prepared by mixing deionized water and anhydrous ethanol with a purity ≥99.7% in a volume ratio of 4:1) until neutral. Then it was dried at 60°C and vacuum degree ≤0.08MPa for 8 h and then ground into a uniform powder to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0076] ICP was used to quantitatively analyze the metal element content of the material prepared in this example. The results showed that the platinum loading was 35.65% by mass, the copper loading was 42.43% by mass, and the total metal loading was 78.08% by mass. Based on this, the platinum-copper atomic ratio was calculated to be approximately 1:3.65. The ORR catalytic performance of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial prepared in Example 6 was tested. The test results showed that the electrochemical area of ​​the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial in Example 6 was 62 m². 2 / g, with a mass activity of 584mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 34%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 37%.

[0077] Comparative Example 1 A method for preparing a carbon-supported platinum-copper material (the metal loading of the carbon-supported platinum-copper material is 77.56% by mass percentage) specifically includes the following steps: (1) Carbon carrier Cabot BP2000 was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Cabot BP2000 added to the dispersion was 3.33 mg / mL. Then, platinum precursor (platinum acetylacetonate) and copper precursor (copper nitrate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 60℃ and magnetic stirring at 500 rpm for 24 h in a constant temperature water bath to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of carbon carrier to platinum precursor of 1:1.5, and the copper precursor was added to the dispersion at a mass ratio of carbon carrier to copper precursor of 1:2.5.

[0078] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0079] (3) The solid composite was placed in a tube furnace and calcined at 900°C for 3 hours at a heating rate of 5°C / min under a high-purity nitrogen atmosphere to reduce the platinum copper and fully alloy it. Then the furnace was cooled to room temperature to obtain a black solid powder, namely carbon-supported platinum copper material.

[0080] According to ICP testing, the material prepared in this comparative example has a platinum loading of 35.43% by mass, a copper loading of 42.13% by mass, and a total metal loading of 77.56% by mass. Based on this, the platinum-copper atomic ratio is calculated to be approximately 1:3.65.

[0081] The ORR catalytic performance of the carbon-supported platinum-copper material prepared in Comparative Example 1 was tested. The results showed that the electrochemical area of ​​the carbon-supported platinum-copper material in Comparative Example 1 was 50 m². 2 / g, with a mass activity of 256mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 64%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 60%.

[0082] Comparative Example 2 A method for preparing a carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion (the metal loading of the carbon-supported platinum-copper all-alloy nanomaterial is 62.59% by mass percentage) specifically includes the following steps: (1) Carbon carrier Cabot BP2000 was dispersed in anhydrous ethanol using an ultrasonic machine with a power of 500W to form a uniform dispersion. The amount of Cabot BP2000 added to the dispersion was 3.33 mg / mL. Then, platinum precursor (platinum acetylacetonate) and copper precursor (copper nitrate) were added to the dispersion and ultrasonically dispersed for 1 h. Then, the dispersion was subjected to constant temperature adsorption treatment at 60℃ and magnetic stirring at 500 rpm for 24 h in a constant temperature water bath to obtain a suspension mixture. The platinum precursor was added to the dispersion at a mass ratio of carbon carrier to platinum precursor of 1:1.5, and the copper precursor was added to the dispersion at a mass ratio of carbon carrier to copper precursor of 1:2.5.

[0083] (2) Evaporate the suspension mixture at 60°C for 2 hours to obtain a homogeneous mixture containing platinum precursor, copper precursor and carbon support. Place the mixture in a vacuum drying oven with a vacuum degree ≤0.08MPa and dry at 60°C for 8 hours. After it is completely dried, grind it into a homogeneous powder to obtain a solid composite.

[0084] (3) The solid composite was placed in a tube furnace and calcined at 750°C for 3 hours under a high-purity nitrogen atmosphere at a heating rate of 5°C / min to reduce the platinum copper and fully alloy it. Then, it was cooled to room temperature with the furnace to obtain a black solid powder, namely carbon-supported platinum copper material.

[0085] (4) The carbon-supported platinum-copper material was placed in a 5 mol / L, 80℃ aqueous acetic acid solution for 16 h to undergo strong acid corrosion treatment to obtain the carbon-supported platinum-copper material after strong acid corrosion treatment. The carbon-supported platinum-copper material after strong acid corrosion treatment was washed with an aqueous ethanol solution (the aqueous ethanol solution was prepared by mixing deionized water and anhydrous ethanol with a purity ≥99.7% in a volume ratio of 4:1) until neutral. Then it was dried at 60℃ and vacuum degree ≤0.08MPa for 8 h and then ground into a uniform powder to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

[0086] According to ICP testing, the material prepared in this comparative example has a platinum loading of 34.43% by mass, a copper loading of 28.16% by mass, and a platinum-copper metal loading of 62.59% by mass. Based on this, the platinum-copper atomic ratio is calculated to be approximately 1:2.51.

[0087] The ORR catalytic performance of the carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion prepared in Comparative Example 2 was tested. The results showed that the electrochemical area of ​​the carbon-supported platinum-copper nanomaterial in Comparative Example 2 was 38 m². 2 / g, with a mass activity of 417mA / mg; after 30,000 cycles of testing in the 0.6~0.95V voltage range, its performance loss rate is 45%, and after 5,000 cycles of testing in the 1.0~1.5V voltage range, its performance loss rate is 43%.

[0088] The X-ray diffraction (XRD) patterns of the materials prepared in Examples 1-3 and Comparative Examples 1-2 of this invention are as follows: Figure 1As shown, the diffraction peaks of the platinum-copper alloy (111) crystal plane of the carbon-supported platinum-copper all-alloy nanomaterial resistant to strong acid corrosion in Example 1 shifted 2.482° towards a higher angle compared to Comparative Example 2, indicating a reduction in interplanar spacing. This is a typical characteristic of lattice shrinkage caused by the alloying of platinum and copper. Compared to Comparative Example 1 without acid treatment, no diffraction peaks of pure copper phase were detected in the XRD pattern of Example 1, and the full width at half maximum (FWHM) of its main diffraction peaks decreased, with a systematic shift in peak position. This indicates that the acid treatment process selectively etched the unalloyed free copper phase, resulting in copper in the catalyst existing only in an alloyed form. The shift in the diffraction peak positions of the etched sample conforms to the lattice constant change law caused by alloying (Vegard's law), and the decrease in FWHM reflects the improvement in phase purity and crystallinity. Therefore, the XRD results directly prove that through the acid etching process, Example 1 successfully eliminated phase-separated pure copper, retaining a fully alloy structure with uniform composition and higher phase purity resistant to high-concentration acid corrosion. This is the key structural basis for obtaining superior oxygen reduction activity and stability. Further phase analysis confirmed that the active component of the catalyst exists in the form of PtCu3 crystalline phase. The XRD results and ICP measurements showed high agreement, jointly confirming that this method successfully prepared a uniformly composed, single-phase structure, acid-resistant platinum-copper all-alloy catalyst. No free metal phase or low-alloyed components were detected, indicating that the process has a significant effect on promoting atomic-level fusion and phase purification of platinum and copper. In Example 2, the diffraction peaks of the platinum-copper alloy (111) crystal plane of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterial shifted 2.624° towards a higher angle compared to the material in Comparative Example 2, indicating a reduction in interplanar spacing. This is a typical characteristic of lattice shrinkage caused by the alloying of platinum and copper. Further phase analysis confirmed that the active component of this material exists in the form of PtCu3 crystalline phase. Compared to Comparative Example 1 without acid treatment, no diffraction peaks of pure copper phase were detected in the XRD pattern of Example 2. This indicates that the strong acid treatment process selectively etched the unalloyed free copper phase, resulting in copper elements existing only in an alloyed form in the material, and that this crystal structure is stable in a strong acid environment. XRD test results of carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion prepared in Example 3 ( Figure 1The XRD pattern shows that the 2θ angle corresponding to the peak of the (111) crystal plane of the platinum-copper alloy is shifted 2.672° to the right compared to the material synthesized by the process in Comparative Example 2, indicating that the active component exists in the form of PtCu3 crystalline phase. Phase analysis of the spectrum shows that the active component of the material synthesized in Example 3 exists in the form of PtCu3 crystalline phase. Compared with Comparative Example 1 without acid treatment, no diffraction peaks of pure copper phase were detected in the XRD pattern of Example 3. This indicates that the acid treatment process selectively etched the unalloyed free copper phase, so that copper elements in the material exist only in alloyed form, and this crystal structure is stable in a strong acid environment. The XRD results are in high agreement with the atomic ratio measured by ICP, jointly confirming that the method of the present invention successfully prepared a uniformly composed, single-phase structure, acid-resistant all-alloyed platinum-copper material, with no detected free metal phase or low-alloyed components, indicating that the process has a significant effect on promoting atomic-level fusion and phase purification of platinum-copper.

[0089] Figure 6 and Figure 7 The cyclic voltammetry (CV) curves and polarization curves (LSV) of the acid-resistant carbon-supported platinum-copper alloy nanomaterials prepared in Examples 2 and 4, respectively, are shown. Based on the test results, the electrochemical active area of ​​Example 2 is calculated to be 61 m². 2 / g, with a mass activity of 866 mA / mg; while the electrochemical active area of ​​Example 4 is 40m². 2 / g, with a mass activity of 564mA / mg.

[0090] Figure 8 and Figure 9 The cyclic voltammetry (CV) curves and polarization curves (LSV) of the acid-resistant carbon-supported platinum-copper alloy nanomaterials prepared in Example 2 and Comparative Example 1, respectively, are shown. Based on the test results, the electrochemical active area of ​​Example 2 is calculated to be 61 m². 2 / g, with a mass activity of 866mA / mg; while the electrochemical active area of ​​Comparative Example 1 is only 50m². 2 / g, with a mass activity of 256mA / mg. This is because strong acid corrosion treatment plays a decisive role in improving the electrochemical performance of the catalyst. Comparative Example 1, which did not undergo strong acid corrosion treatment, had a large amount of incompletely alloyed or structurally unstable platinum-copper components remaining in the material. These non-alloyed components, on the one hand, cover or block the active sites of the catalyst, resulting in a low effective electrochemical active area; on the other hand, these unstable components are prone to dissolution or structural reconstruction during electrochemical testing, which not only reduces the utilization rate of platinum atoms but also weakens the intrinsic activity of the catalytic reaction, thus reducing the mass activity.

[0091] Figure 10 and Figure 11The CV curves and polarization curves (LSVs) of the acid-resistant carbon-supported platinum-copper alloy nanomaterials prepared in Example 2 and Comparative Example 2, respectively, are obtained by cyclic voltammetry testing. Based on the test results, the electrochemical active area of ​​Example 2 is calculated to be 61 m². 2 / g, with a mass activity of 866mA / mg, and the electrochemical active area of ​​Comparative Example 2 is 38m². 2 The activity was 417 mA / mg. This indicates that heat treatment temperature is a key factor in the preparation of high-performance catalysts. Comparative Example 2, due to thermal reduction at a lower temperature, suffered from insufficient thermal driving force, leading to reduced reduction efficiency of the platinum-copper bimetallic precursor, inadequate atomic diffusion and intermetallic integration, and difficulty in forming a highly alloyed platinum-copper structure. This incomplete alloying process left a large amount of unalloyed elemental components and low-alloy defect phases in the material. Although subsequent strong acid corrosion treatment was performed, the removal of these unstable unalloyed components resulted in a limited number of highly alloyed platinum-copper phases, leading to sparse effective active sites and a low electrochemical active area on the catalyst surface. Simultaneously, due to insufficient alloying, the electronic regulation between platinum and copper was weak, making it difficult to effectively optimize the intrinsic activity of platinum in the oxygen reduction reaction, thus resulting in poor mass activity.

[0092] Combination Figures 6-11 It can be concluded that the carbon-supported platinum-copper alloy nanomaterial resistant to strong acid corrosion prepared in the embodiments of the present invention has a larger electrochemical active area and higher oxygen reduction catalytic activity.

[0093] Figure 12 and Figure 13 The figures show the electrochemical active area and mass activity of the acid-resistant carbon-supported platinum-copper alloy nanomaterial prepared in Example 2 after durability testing within the potential range of 0.6–1.0 V. The test results show that the electrochemical active area did not decrease after the test, and the mass activity decreased only slightly, indicating that Example 2 exhibits excellent stability.

[0094] The XRD results of the acid-resistant carbon-supported platinum-copper all-alloy nanomaterials prepared in Examples 4-6 of this invention are in high agreement with the atomic ratios measured by ICP. Together, they confirm that the method of this invention has successfully prepared platinum-copper all-alloy materials with uniform composition and simple phase structure. No free metal phase or low-alloyed components were detected, indicating that the process has a significant effect on promoting atomic-level fusion and phase purification of platinum and copper.

[0095] TEM tests were performed on the acid-resistant carbon-supported platinum-copper all-alloy nanomaterials prepared in Examples 1, 4-6. The tests showed that Examples 1, 4-6 achieved the deposition of uniformly dispersed PtCu nanoparticles on the surface of a conductive carbon support.

[0096] XPS tests were performed on the carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion prepared in Examples 4-6. The negative shift of the Pt 4f binding energy and the positive shift of the Cu 2p binding energy in the test results indicate that there is a strong electronic interaction between Pt and Cu. Electrons are transferred from Cu (low electronegativity) to Pt (high electronegativity), which modulates the adsorption energy of oxygen-containing intermediates on the surface, thereby improving the catalytic activity of the material.

[0097] The carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion prepared in this invention exhibit a complete alloy crystal structure, high metal loading, and a clean alloy surface under the synergistic effect of alloying and strong acid corrosion treatment. They also show significantly enhanced catalytic activity and long-term stability in oxygen reduction reactions.

[0098] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or improvement of the technology in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion, characterized in that, Specifically, the following steps are included: (1) The carbon support is dispersed in a solvent to form a dispersion, and then the platinum precursor and copper precursor are added to the dispersion and dispersed. Then, the constant temperature adsorption treatment is carried out to obtain a suspension mixture. (2) The suspension mixture was evaporated to dryness to obtain a mixture containing platinum precursor, copper precursor and carbon support. The mixture was dried and ground to obtain a solid composite. (3) The solid composite was calcined under an inert atmosphere and then cooled to obtain a carbon-supported platinum-copper material; (4) The carbon-supported platinum-copper material is placed in a strong acid solution for strong acid corrosion resistance treatment to obtain the carbon-supported platinum-copper material after strong acid corrosion resistance treatment. The carbon-supported platinum-copper material after strong acid corrosion resistance treatment is washed, dried and ground to obtain the carbon-supported platinum-copper full alloy nanomaterial resistant to strong acid corrosion.

2. The method for preparing the strong acid-resistant carbon-supported platinum-copper all-alloy nanomaterial according to claim 1, characterized in that, The solvent in step (1) is anhydrous ethanol; the amount of carbon support added in the dispersion is 2~6 mg / mL.

3. The method for preparing the strong acid-resistant carbon-supported platinum-copper all-alloy nanomaterial according to claim 1, characterized in that, In step (1), the carbon support is one of Ketjen Black EC-300J, Ketjen Black EC-600J, Cabot BP2000 or Cabot XC-72.

4. The method for preparing the strong acid-resistant carbon-supported platinum-copper all-alloy nanomaterial according to claim 1, characterized in that, In step (1), the platinum precursor is one of chloroplatinic acid, platinum acetylacetonate, platinum chloride, platinum nitrate, ethanolamine hydroxyplatinum, and dihydroxytetramineplatinum; the copper precursor is one of copper acetylacetonate, copper chloride, copper nitrate, and copper sulfate.

5. The method for preparing the strong acid-resistant carbon-supported platinum-copper all-alloy nanomaterial according to claim 1, characterized in that, In step (1), the platinum precursor is added to the dispersion at a mass ratio of carbon support to platinum precursor of 1:(1~4); the copper precursor is added to the dispersion at a mass ratio of carbon support to copper precursor of 1:(2~6).

6. The method for preparing the strong acid-resistant carbon-supported platinum-copper all-alloy nanomaterial according to claim 1, characterized in that, The conditions for the isothermal adsorption treatment in step (1) are: isothermal adsorption at 60~80℃ for 18~30h.

7. The method for preparing the strong acid-resistant carbon-supported platinum-copper all-alloy nanomaterial according to claim 1, characterized in that, The inert atmosphere in step (3) is nitrogen or argon; the calcination conditions are: heating to 800-1100℃ at a heating rate of 1-50℃ / min and holding for 3-10h.

8. The method for preparing the strong acid-resistant carbon-supported platinum-copper all-alloy nanomaterial according to claim 1, characterized in that, The strong acid solution in step (4) is one or more of acetic acid, sulfuric acid or nitric acid aqueous solution; the concentration of the strong acid solution is 5~10 mol / L; the temperature of the strong acid solution is 60~90℃; and the time of the strong acid corrosion resistance treatment is 10~18h.

9. Carbon-supported platinum-copper all-alloy nanomaterials resistant to strong acid corrosion prepared by the method according to any one of claims 1 to 8.

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