S-rucr / c composite material and preparation method and application thereof

Abstract

This invention relates to the field of fuel cell technology, and more particularly to an S-RuCr / C composite material, its preparation method, and its applications. The invention involves mixing a ruthenium source, a chromium source, a sulfur source, a hollow carbon sphere support, and a solvent, followed by a hydrothermal reaction to obtain an S-RuCr / C composite material precursor. The precursor is then calcined under a mixed atmosphere of hydrogen and argon to obtain the S-RuCr / C composite material. The preparation method of this invention is simple, as the hydrothermal reaction does not require the high temperatures of solid-state reactions (typically 800–1200°C), meeting the requirements of green chemistry and low energy consumption. Furthermore, it exhibits excellent electrocatalytic hydrogenation performance under alkaline conditions. Therefore, the S-RuCr / C composite material prepared by this invention has promising potential applications in anion exchange membrane fuel cells.

Description

Technical Field

[0001] This invention relates to the field of fuel cell technology, and in particular to an S-RuCr / C composite material, its preparation method, and its applications. Background Technology

[0002] Hydrogen, as a highly promising low-carbon energy carrier, offers a crucial path to solving the current dual dilemma of energy shortage and environmental degradation due to its excellent energy density, green sustainability, and environmentally friendly properties. The core of building an efficient and sustainable hydrogen energy cycle system lies in hydrogen production and conversion processes. Among these, anion exchange membrane fuel cells (AEMFCs), as a novel technological approach, demonstrate enormous application potential: they hold the promise of completely eliminating dependence on scarce and expensive platinum-based catalysts, opening a new technological paradigm for achieving zero-carbon energy supply. Although a series of non-precious metal catalysts have achieved breakthroughs in the cathode oxygen reduction reaction (ORR) of AEMFCs, the kinetics of the anodic hydrogen oxidation reaction (HOR) remain sluggish under alkaline conditions, requiring the equipment to rely on high platinum content to maintain normal performance. This factor has become a core bottleneck restricting the commercial application of AEMFC technology. Therefore, developing electrocatalysts that combine low cost and high performance is of vital practical significance and engineering value for promoting the substantial development of anion exchange membrane fuel cells. Summary of the Invention

[0003] The purpose of this invention is to provide an S-RuCr / C composite material, its preparation method, and its application, in order to solve the problems existing in the prior art.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: One of the technical solutions of this invention provides a method for preparing S-RuCr / C composite materials, comprising the following steps: (1) A ruthenium source, chromium source, sulfur source, hollow carbon sphere support and solvent are mixed and subjected to hydrothermal reaction to obtain S-RuCr / C composite material precursor; (2) The S-RuCr / C composite material precursor was calcined in a mixed atmosphere of hydrogen and argon to obtain the S-RuCr / C composite material.

[0005] The second technical solution of the present invention provides an S-RuCr / C composite material prepared by the above-mentioned preparation method.

[0006] The third technical solution of this invention provides the application of the above-mentioned S-RuCr / C composite material as a hydroxide electrocatalyst in anion exchange membrane fuel cells.

[0007] Compared with the prior art, the present invention has the following beneficial effects: This invention introduces the oxygen-loving element Cr through a one-step hydrothermal method. The introduction of Cr optimizes the electronic structure and surface oxygen-loving properties of the material, enhancing catalytic activity and stability. The overall process aligns with the principles of green chemistry. The S support in the composite material not only effectively disperses the active components but also reduces the catalyst particle diameter. Furthermore, this composite material exhibits excellent electrocatalytic hydrogenation performance under alkaline conditions. Therefore, the S-RuCr / C composite material prepared in this invention shows promising potential applications in anion exchange membrane fuel cells.

[0008] The preparation method of this invention is simple, and the hydrothermal reaction does not require the high temperatures of solid-state reactions (typically 800-1200℃), meeting the requirements of green chemistry and low energy consumption. Furthermore, it exhibits excellent electrocatalytic hydrogenation performance under alkaline conditions. Therefore, the S-RuCr / C composite material prepared by this invention has promising potential applications in anion exchange membrane fuel cells. Attached Figure Description

[0009] Figure 1 X-ray powder diffraction pattern of the carrier C prepared in Example 1; Figure 2 X-ray powder diffraction pattern of the S-Cr / C composite material prepared in Comparative Example 1; Figure 3 X-ray powder diffraction pattern of the S-Ru / C composite material prepared in Comparative Example 2; Figure 4 X-ray powder diffraction pattern of the S-RuCr / C composite material prepared in Example 1; Figure 5 (a) and (b) are transmission electron microscope images of S-RuCr / C prepared in Example 1, (c) is the measured lattice fringes, and (d) is a high-angle annular dark-field transmission electron microscope image. Figure 6 Transmission electron microscope image of the RuCr / C composite material prepared for Comparative Example 7.

[0010] Figure 7 X-ray photoelectron spectra of the S-RuCr / C composite material prepared in Example 1 and the S-Cr / C prepared in Comparative Example 1. Figure 8 X-ray photoelectron spectra of Ru3p of the S-RuCr / C composite material prepared in Example 1 and the S-Ru / C composite material prepared in Comparative Example 2; Figure 9 S 2p X-ray photoelectron spectra of the S-RuCr / C composite material prepared in Example 1, the S-Cr / C composite material prepared in Comparative Example 1, and the S-Ru / C composite material prepared in Comparative Example 2. Figure 10 Linear scanning curves of electrocatalytic hydrogenation of S-RuCr / C composite materials prepared at different annealing temperatures under alkaline conditions for Example 1, Comparative Example 3, and Comparative Example 4; Figure 11 Linear scanning curves of electrocatalytic hydrogenation of S-RuCr / C composite materials with different Cr addition amounts prepared in Example 1, Comparative Example 5, and Comparative Example 6 under alkaline conditions; Figure 12 Linear scanning curves of electrocatalytic oxidation of S-RuCr / C composite material prepared in Example 1, S-Cr / C prepared in Comparative Example 1 and S-Ru / C prepared in Comparative Example 2, and commercial Pt / C under alkaline conditions in 0.1 M KOH solution.

[0011] Figure 13 The long-term stability curves of electrocatalytic hydrogenation of the S-RuCr / C composite material prepared in Example 1, the S-Cr / C composite material prepared in Comparative Example 1, the S-Ru / C composite material prepared in Comparative Example 2, and commercial Pt / C under alkaline conditions are shown. Detailed Implementation

[0012] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0013] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0014] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0015] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This application specification and embodiments are merely exemplary.

[0016] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0017] All raw materials used in this invention can be obtained commercially or prepared using existing technologies.

[0018] All room temperatures mentioned in this invention are calculated as 25±2℃.

[0019] This invention provides a method for preparing S-RuCr / C composite materials, comprising the following steps: (1) A ruthenium source, chromium source, sulfur source, hollow carbon sphere support and solvent are mixed and subjected to hydrothermal reaction to obtain S-RuCr / C composite material precursor; (2) The S-RuCr / C composite material precursor was calcined in a mixed atmosphere of hydrogen and argon to obtain the S-RuCr / C composite material.

[0020] Step (1) of this invention involves adding a ruthenium source, a chromium source, and a hollow carbon sphere support to a solvent and mixing them, then adding a sulfur source, mixing them, and carrying out a hydrothermal reaction. After the reaction is completed, the mixture is cooled to room temperature, centrifuged, washed, and dried to obtain the S-RuCr / C composite material precursor.

[0021] In this invention, the ruthenium source, chromium source, and sulfur source can be selected from compounds with excellent water solubility. In a preferred embodiment of this invention, the ruthenium source includes ruthenium chloride; the chromium source includes chromium nitrate; and the sulfur source includes sodium sulfide.

[0022] In this invention, the molar ratio of the ruthenium source, chromium source and sulfur source is 0.08~0.12:0.1:0.25, for example, it can be 0.08:0.1:0.25, 0.1:0.1:0.25 or 0.12:0.1:0.25, etc.

[0023] In this invention, the ratio of the ruthenium source to the hollow carbon sphere carrier is 0.08~0.12 mmol:30 mg, for example, it can be 0.08 mmol:30 mg, 0.1 mmol:30 mg or 0.12 mmol:30 mg, etc.

[0024] In this invention, the solvent is a mixed solution of ethanol and water; the volume ratio of ethanol to water is 1:1; and the ratio of the hollow carbon sphere carrier to the solvent is 30 mg: 30 mL.

[0025] In this invention, the method for preparing the hollow carbon sphere support includes the following steps: S1. Mix ammonia, silicon source and solvent, stir for 1 hour to obtain solution A; S2. Mix dopamine hydrochloride with a solvent to obtain solution B; S3. Mix solution A and solution B and stir for 12 hours. Wash and dry the resulting product to obtain SiO2 / DA. S4. Anneal SiO2 / DA under a protective atmosphere, etch the resulting product, and centrifuge and dry it to obtain a hollow carbon sphere support.

[0026] In this invention, the silicon source is tetraethyl orthosilicate (TEOS); the volume ratio of ammonia to silicon source is 1:1; the solvent in step S1 is a mixed solution of anhydrous ethanol and water; the volume ratio of anhydrous ethanol to water is 10:3.

[0027] In this invention, the ratio of dopamine hydrochloride to solvent is 500 mg: 75 mL.

[0028] In this invention, the volume ratio of solution A to solution B in step S3 is 28:15.

[0029] In this invention, the washing in step S3 is done with water and ethanol, and the drying temperature is 60°C.

[0030] In this invention, the annealing temperature in step S4 is 800°C, the time is 3 hours, and the protective atmosphere includes nitrogen.

[0031] In this invention, the etching is performed using a high-concentration sodium hydroxide solution for 24 hours.

[0032] In this invention, the temperature of the hydrothermal reaction is 150~170℃, for example, 150℃, 155℃, 160℃, 165℃ or 170℃, etc., and the time is 11~13h, for example, 11h, 12h or 13h.

[0033] In this invention, the calcination temperature is 480~520℃, for example, it can be 480℃, 490℃, 500℃, 510℃ or 520℃, etc., and the holding time is 2h; the volume ratio of hydrogen to argon is 1:9.

[0034] The present invention also provides an S-RuCr / C composite material prepared by the above-described preparation method.

[0035] The present invention also provides the application of the above-mentioned S-RuCr / C composite material as a hydroxide electrocatalyst in anion exchange membrane fuel cells.

[0036] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0037] Example 1 S1. Preparation of carbon support: (1) Add 5 mL of ammonia water to a mixed solution of ethanol and water (anhydrous ethanol: water = 100 mL: 30 mL), then add 5 mL of LTEOS to the above solution and stir for 1 hour to obtain solution A; (2) Dissolve 500 mg of dopamine hydrochloride in 65 mL of a mixed solution (anhydrous ethanol: water = 50 mL: 15 mL) to obtain solution B; (3) Mix solution A and solution B and stir at room temperature for 12 h. Wash the sample with water and ethanol and collect it. Dry it at 60 °C to obtain SiO2 / DA.

[0038] (4) After annealing SiO2 / DA in a nitrogen atmosphere at 800 °C for 3 h, it was etched with 3 mol / L NaOH solution for 24 h, and then centrifuged and dried to obtain carbon support, which was denoted as C; Preparation of S2. S-RuCr / C composite material: (1) 30 mg of carrier, 0.1 mmol RuCl3 hydrate, and 0.1 mmol Cr(NO3)3·9H2O were placed in a 100 ml reactor, 30 mL of mixed solution (EtOH:H2O=1:1) was added, and 0.25 mmol Na2S·9H2O was added. The mixture was stirred for 30 min, and then reacted solvothermically at 160 °C for 12 h. After centrifugation and washing, the mixture was dried at 60 °C to obtain the S-RuCr / C composite material precursor. (2) The S-RuCr / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (volume ratio of H2 to N2 is 1:9) at a heating rate of 5 ℃ / min to 500 ℃ to obtain the S-RuCr / C composite material.

[0039] Comparative Example 1 S1. Same as Example 1; Preparation of S2. S-Cr / C composite materials: (1) 30 mg of carrier and 0.1 mmol of Cr(NO3)3·9H2O were placed in a 100 ml reactor, 30 mL of mixed solution (EtOH:H2O=1:1) were added, 0.25 mmol of Na2S·9H2O were added, the mixture was stirred for 30 min, and then the reaction was carried out at 160 °C for 12 h in a solvothermal environment. After centrifugation and washing, the mixture was dried at 60 °C to obtain the S-Cr / C composite material precursor. (2) The S-Cr / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (H2 and N2 volume ratio of 1:9) at a heating rate of 5 ℃ / min to 500 ℃ to obtain the S-Cr / C composite material.

[0040] Comparative Example 2 S1. Same as Example 1; Preparation of S2.S-Ru / C composite materials: (1) 30 mg of carrier and 0.1 mmol of RuCl3 hydrate were placed in a 100 ml reactor, 30 mL of mixed solution (EtOH:H2O=1:1) were added, 0.25 mmol of Na2S·9H2O was added, the mixture was stirred for 30 min, and then the reaction was carried out at 160 °C for 12 h in a solvothermal environment. After centrifugation and washing, the mixture was dried at 60 °C to obtain the S-Ru / C composite material precursor. (2) The S-Ru / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (H2 and N2 volume ratio of 1:9) at a heating rate of 5 ℃ / min to 500 ℃ to obtain the S-Ru / C composite material.

[0041] Comparative Example 3 S1. Same as Example 1; Preparation of S2. S-RuCr / C composite material: (1) 30 mg of carrier, 0.1 mmol RuCl3 hydrate, and 0.1 mmol Cr(NO3)3·9H2O were placed in a 100 ml reactor, 30 mL of mixed solution (EtOH:H2O=1:1) was added, and 0.25 mmol Na2S·9H2O was added. The mixture was stirred for 30 min, and then reacted solvothermically at 160 °C for 12 h. After centrifugation and washing, the mixture was dried at 60 °C to obtain the S-RuCr / C composite material precursor. (2) The S-RuCr / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (volume ratio of H2 to N2 is 1:9) at a heating rate of 5℃ / min to 450℃ to obtain the S-RuCr / C composite material.

[0042] Comparative Example 4 S1. Same as Example 1; Preparation of S2. S-RuCr / C composite material: (1) 30 mg of carrier, 0.1 mmol RuCl3 hydrate, and 0.1 mmol Cr(NO3)3·9H2O were placed in a 100 ml reactor, 30 mL of mixed solution (EtOH:H2O=1:1) was added, and 0.25 mmol Na2S·9H2O was added. The mixture was stirred for 30 min, and then reacted solvothermically at 160 °C for 12 h. After centrifugation and washing, the mixture was dried at 60 °C to obtain the S-RuCr / C composite material precursor. (2) The S-RuCr / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (H2 and N2 volume ratio of 1:9) at a heating rate of 5 ℃ / min to 550 ℃ to obtain the S-RuCr / C composite material.

[0043] Comparative Example 5 S1. Same as Example 1; Preparation of S2.S-RuCr / C composite materials: (1) 30 mg of carrier, 0.1 mmol of RuCl3 hydrate, and 0.05 mmol of Cr(NO3)3·9H2O were placed in a 100 ml reactor, 30 mL of mixed solution (EtOH:H2O=1:1) were added, and 0.25 mmol of Na2S·9H2O was added. The mixture was stirred for 30 min, and then reacted solvothermically at 160 °C for 12 h. After centrifugation and washing, the mixture was dried at 60 °C to obtain the S-RuCr / C composite material precursor. (2) The S-RuCr / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (volume ratio of H2 to N2 is 1:9) at a heating rate of 5 ℃ / min to 500 ℃ to obtain the S-RuCr / C composite material.

[0044] Comparative Example 6 S1. Same as Example 1; Preparation of S2.S-RuCr / C composite materials: (1) 30 mg of carrier, 0.1 mmol RuCl3 hydrate, and 0.15 mmol Cr(NO3)3·9H2O were placed in a 100 ml reactor, 30 mL of mixed solution (EtOH:H2O=1:1) were added, and 0.25 mmol Na2S·9H2O was added. The mixture was stirred for 30 min, and then reacted solvothermically at 160 °C for 12 h. After centrifugation and washing, the mixture was dried at 60 °C to obtain the S-RuCr / C composite material precursor. (2) The S-RuCr / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (volume ratio of H2 to N2 is 1:9) at a heating rate of 5 ℃ / min to 500 ℃ to obtain the S-RuCr / C composite material.

[0045] Comparative Example 7 S1. Same as Example 1; Preparation of S2.RuCr / C composite materials: (1) 30 mg of carrier, 0.1 mmol of RuCl3 hydrate, and 0.15 mmol of Cr(NO3)3·9H2O were placed in a 100 ml reactor, and 30 mL of mixed solution (EtOH:H2O=1:1) was added. The mixture was stirred for 30 min, and then reacted solvothermically at 160 °C for 12 h. After centrifugation and washing, the mixture was dried at 60 °C to obtain the RuCr / C composite material precursor. (2) The RuCr / C composite material precursor was annealed for 2 h in an H2 / N2 atmosphere (volume ratio of H2 to N2 is 1:9) at a heating rate of 5 ℃ / min to 500 ℃ to obtain the RuCr / C composite material.

[0046] Figure 1 The X-ray powder diffraction pattern of the support C prepared in Example 1 is shown below. Figure 1 The successful synthesis of vector C can be seen from this.

[0047] Figure 2 The image shows the X-ray powder diffraction pattern of the S-Cr / C composite material prepared in Comparative Example 1. Figure 1 In contrast, there are no obvious diffraction peaks, indicating that Cr exists in an amorphous state.

[0048] Figure 3 The X-ray powder diffraction pattern of S-Ru / C prepared in Comparative Example 2 is shown below. Figure 3 The diffraction peaks show a good match with the Ru standard card (06-0663), indicating the successful synthesis of Ru / C.

[0049] Figure 4 The X-ray powder diffraction pattern of the S-RuCr / C composite material prepared in Example 1; from Figure 4 As can be seen from the data, all diffraction peaks can be indexed as S-RuCr / C, indicating the successful synthesis of S-RuCr / C.

[0050] Figure 5Images (a) and (b) are transmission electron microscope (TEM) images of the S-RuCr / C prepared in Example 1. Image (a) shows that the catalyst particles are uniformly dispersed and have a small particle size. Image (c) shows the measured lattice fringes. Image (d) is a high-angle annular dark-field TEM image of the S-RuCr / C composite material prepared in Example 1, demonstrating that the elements are uniformly distributed in the composite material.

[0051] Figure 6 The transmission electron microscope image of RuCr / C prepared in Comparative Example 7 shows that the catalyst particles are unevenly dispersed and have a large particle size, illustrating the effect of the introduction of S on the catalyst morphology.

[0052] Figure 7 The X-ray photoelectron spectra of the S-RuCr / C composite material prepared in Example 1 and the Cr 2p X-ray photoelectron spectra of the S-Cr / C composite material prepared in Comparative Example 1 demonstrate the successful introduction of Cr.

[0053] Figure 8 The Ru3p X-ray photoelectron spectra of the S-RuCr / C composite material prepared in Example 1 and the S-Ru / C composite material prepared in Comparative Example 2 demonstrate that the electronic structure of Ru can be effectively adjusted after the introduction of Cr, thereby improving the catalytic performance of the S-RuCr / C composite material.

[0054] Figure 9 S 2p X-ray photoelectron spectra of the S-RuCr / C composite material prepared in Example 1, the S-Cr / C composite material prepared in Comparative Example 1, and the S-Ru / C composite material prepared in Comparative Example 2. This figure illustrates the successful introduction of S element, and that S element exists in the catalyst in the form of a dopant.

[0055] The electrochemical hydrogenation test in this invention was performed using a three-electrode system on an electrochemical workstation (Shanghai CHI 760E and US PINE). The composite materials prepared in each example and comparative example were dropped onto a glassy carbon electrode as the working electrode, a carbon rod as the counter electrode, a saturated silver silver chloride electrode as the reference electrode, and a 0.1 mol / L potassium hydroxide solution as the electrolyte. The test temperature was 25 °C, the scan rate was 10 mV / s, and the electrode potential was obtained by using a saturated silver silver chloride electrode and corrected for a reversible hydrogen electrode (RHE). All hydrogenation potentials in this invention were obtained according to the Nernst equation (1): Hydroxylation potential = E Ag / AgCl +0.197+0.059×pH-iR (1) The method for determining the catalytic performance of different composite materials in this invention is as follows: To fabricate a thin-film working electrode, 3 mg of the sample prepared in the examples or comparative examples was ultrasonically dispersed with 15 μL of Nafion solution (5 wt.%) in 490 μL of deionized water-isopropanol solution (volume ratio 1:1) to form a uniform ink. Then, 10 μL of the fully dispersed catalyst ink was suspended on a pre-polished glassy carbon electrode, and the ink was dried before measurement.

[0056] The method for determining the stability of different composite materials in this invention is as follows: the measurement is performed in an H2-saturated atmosphere at a rotation rate of 1600 revolutions per minute (rpm) of a rotating disk electrode (RDE).

[0057] Figure 10 The linear scanning curves of electrocatalytic hydrogenation of the S-RuCr / C composite materials prepared in Examples 1 and Comparative Examples 3-4 show that the composite material with the best catalytic performance is obtained when the amount of Cr added is 0.01 mmol and the temperature is fixed at 500 °C.

[0058] Figure 11 Linear scanning curves of electrocatalytic hydrogenation of the S-RuCr / C composite materials prepared in Examples 1, 5, and 6 show that the composite material exhibits the best catalytic performance when the amount of Cr added is 0.1 mmol, while the catalytic performance decreases when the amount of Cr added is 0.05 mmol or 0.15 mmol.

[0059] Figure 12 Linear scanning curves of electrocatalytic hydrogenation of the S-RuCr / C composite material prepared in Example 1, the S-Cr / C prepared in Comparative Example 1 and Comparative Example 2, and commercial Pt / C are shown. Compared with other comparative catalysts, the S-RuCr / C composite material prepared in this invention has the best catalytic performance.

[0060] Figure 13 The table shows the long-term stability curves of the S-RuCr / C composite material prepared in Example 1, the S-Ru / C prepared in Comparative Example 2, and commercial Pt / C under alkaline conditions for electrocatalytic hydrogenation. Compared with other comparative catalysts, the S-RuCr / C composite material prepared in this invention has the best stability.

[0061] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing an S-RuCr / C composite material, characterized in that, Includes the following steps: (1) A ruthenium source, chromium source, sulfur source, hollow carbon sphere support and solvent are mixed and subjected to hydrothermal reaction to obtain S-RuCr / C composite material precursor; (2) The S-RuCr / C composite material precursor was calcined in a mixed atmosphere of hydrogen and argon to obtain the S-RuCr / C composite material.

2. The preparation method according to claim 1, characterized in that, The ruthenium source includes ruthenium chloride; the chromium source includes chromium nitrate; and the sulfur source includes sodium sulfide.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the ruthenium source, chromium source and sulfur source is 0.08~0.12:0.1:0.

25.

4. The preparation method according to claim 1, characterized in that, The ratio of the ruthenium source to the hollow carbon sphere carrier is 0.08~0.12 mmol: 30 mg.

5. The preparation method according to claim 1, characterized in that, The hydrothermal reaction is carried out at a temperature of 150-170°C for 11-13 hours.

6. The preparation method according to claim 1, characterized in that, The calcination temperature is 480~520℃, and the holding time is 2h; the volume ratio of hydrogen to argon is 1:

9.

7. The S-RuCr / C composite material prepared by the preparation method according to any one of claims 1 to 6.

8. The application of the S-RuCr / C composite material of claim 7 as a hydroxide electrocatalyst in anion exchange membrane fuel cells.

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