Ruthenium group cluster hydrogen oxidation electrocatalyst for resisting CO poisoning as well as preparation method and application of ruthenium group cluster hydrogen oxidation electrocatalyst
By supporting ruthenium cluster catalysts on nitrogen-oxygen co-doped carbon materials modified with indium single atoms, the problems of insufficient activity and easy poisoning of ruthenium-based catalysts in alkaline media are solved, achieving a balance between high activity and stability, which is suitable for the commercialization of fuel cell catalysts.
Patent Information
- Application Number
- CN202511785838.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-01
- Publication Date
- 2026-03-24
AI Technical Summary
Existing ruthenium-based catalysts have insufficient intrinsic HOR activity in alkaline media and are susceptible to CO poisoning, making it difficult to achieve a balance between high activity, strong resistance to poisoning, and long-term stability.
Using indium single-atom modified nitrogen-oxygen co-doped carbon material as a support, ruthenium cluster catalyst is loaded. Through the single-atom-cluster synergistic structure formed by indium and ruthenium, electronic regulation is achieved, thereby improving catalytic activity and resistance to CO poisoning.
The catalyst exhibits high activity and excellent resistance to CO poisoning in alkaline media, and has good structural stability, making it suitable for large-scale preparation and commercial application.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of new energy and new materials, and particularly relates to a ruthenium-based cluster hydro-oxidation electrocatalyst resistant to CO poisoning and a preparation method and application thereof. BACKGROUND
[0002] Hydrogen energy, as a clean and efficient secondary energy, has outstanding advantages such as high energy density and zero carbon emission in the utilization process, and is an important part of building a future low-carbon energy system. Hydrogen fuel cell is the core device for efficient utilization of hydrogen energy, and has great application potential in the fields of transportation (fuel cell vehicles), distributed power generation, industrial standby power supply, etc. The hydrogen oxidation reaction (HOR) occurring at the anode of the hydrogen fuel cell is slow in kinetics and highly dependent on noble metal catalysts such as platinum (Pt). However, in practical applications, especially when there are trace amounts of carbon monoxide (CO) impurities in the hydrogen fuel, the active sites of the Pt catalyst will be quickly poisoned and deactivated due to the strong adsorption of CO, which seriously restricts the long-term stability and commercialization process of the fuel cell.
[0003] In order to solve the CO poisoning problem of the Pt catalyst, researchers have turned their attention to ruthenium (Ru)-based catalysts which are less expensive. Since the adsorption energy of Ru on CO is lower than that of Pt, Ru theoretically has better anti-poisoning potential. However, the existing Ru-based catalysts still have significant shortcomings: on the one hand, Ru nanoparticles will still be slowly accumulated and poisoned by the weak adsorption of CO during long-term operation, and are prone to oxidation and agglomeration, resulting in a decrease in activity; on the other hand, the intrinsic HOR activity of Ru in alkaline medium still needs to be improved. Therefore, developing a low-cost HOR catalyst with high intrinsic activity, excellent stability and excellent anti-CO poisoning ability is still a key technical problem to be solved in the field.
[0004] Based on the above technical difficulties, an ideal hydrogen oxidation reaction (HOR) catalyst needs to meet several stringent requirements: first of all, it must have excellent intrinsic anti-poisoning ability to effectively resist the poisoning effect of impurities such as carbon monoxide (CO); secondly, it needs to exhibit high intrinsic catalytic activity in alkaline medium, for example, it has an optimal hydrogen adsorption free energy ( ) close to the optimal value; in addition, it also needs to have long-term structural stability to prevent oxidation, loss or agglomeration of the active components. However, the existing catalyst systems, including advanced ruthenium (Ru)-based catalysts, are difficult to achieve a good balance among the above-mentioned performances.
[0005] Therefore, breaking through the limitations of existing catalyst design and developing a new type of HOR catalyst that can balance high activity, strong anti-poisoning and excellent stability has become the key to promoting the development of hydrogen fuel cell technology, which is also the fundamental starting point and core purpose of the present application. SUMMARY
[0006] To solve the above technical problems, the main purpose of the present application is to provide a ruthenium-based cluster hydroxidation electrocatalyst resistant to CO poisoning and a preparation method and application thereof.
[0007] To achieve the above-mentioned purpose, in one aspect, the present application provides a ruthenium-based cluster hydroxidation electrocatalyst resistant to carbon monoxide (CO) poisoning, which is in an ultrathin sheet structure, and has an indium (In) single atom modified nitrogen-oxygen co-doped carbon material as a carrier and a ruthenium (Ru) cluster as an active center loaded on the carrier; wherein, based on the total mass of the catalyst, the loading amount of the indium single atom is 0.5-3 wt%, and the loading amount of the ruthenium cluster is 5-15 wt%.
[0008] The indium single atom is stably anchored in the carbon carrier in an atomic dispersion form, and exists stably by forming a coordination bond (such as In-N3O1 structure) with nitrogen and oxygen atoms in the carrier. The ruthenium cluster is distributed on the surface of the carrier in a highly dispersed state, and the average particle size is 1-3 nanometers. Through this "single atom-cluster" synergistic structure, the indium site can produce a significant electronic regulation effect on the adjacent ruthenium cluster, optimize the adsorption energy of the reaction intermediate, which is the structural basis for realizing high activity and strong anti-poisoning ability.
[0009] According to a second aspect of the present application, the present application provides a preparation method of a ruthenium-based cluster hydroxidation electrocatalyst resistant to CO poisoning, which comprises the following steps:
[0010] (1) Preparation of an indium single atom modified nitrogen-doped carbon carrier:
[0011] This stage realizes the single atom dispersion of In through a molecular level precursor design and a controllable pyrolysis process. Specifically, glucose, dicyanediamine and indium salt are dissolved in a solvent to form a molecularly uniform precursor mixed solution; then, the molecularly dispersed state is "solidified" in a solid precursor through evaporation concentration and freeze-drying technology; finally, the solid precursor is subjected to a first calcination treatment at 800-1100℃ under an inert atmosphere, in which process, glucose and dicyanediamine are pyrolyzed to form a nitrogen-oxygen co-doped carbon skeleton, and the indium precursor is coordinated with heteroatoms, thereby stably anchoring in the carbon carrier in the form of a single atom.
[0012] (2) Loading and activation of the ruthenium cluster:
[0013] The stage realizes high dispersion loading of Ru clusters on the constructed In single-atom carrier through liquid-phase impregnation and mild reduction strategy. Specifically, the carrier obtained in the first stage is dispersed in a solvent, and impregnated with a ruthenium salt solution to capture and fix ruthenium ions by using the functional groups on the surface of the carrier; after impregnation, drying treatment is performed, and then second calcination treatment is performed at 300-500 DEG C in a reducing atmosphere to controllably reduce the ruthenium ions into metal Ru clusters, and finally form a stable Ru-based cluster hydro-oxidation electrocatalyst Ru AC / In1@CNO.
[0014] As a further preferred technical solution of the present application, the solvent of the precursor mixed solution is water, the temperature of evaporation and concentration is 80-100 DEG C, and the indium salt is selected from indium nitrate or indium chloride.
[0015] As a further preferred technical solution of the present application, the mass ratio of the glucose, dicyandiamide and indium salt is 1:20:0.0095-0.057.
[0016] As a further preferred technical solution of the present application, the temperature of the first calcination is 800-1100 DEG C, the heating rate is ≤5 DEG C / min, and the holding time is 1-3 hours.
[0017] As a further preferred technical solution of the present application, the impregnation time is 12-36 hours.
[0018] As a further preferred technical solution of the present application, the second calcination is performed in an H2 and Ar atmosphere, the volume ratio of H2 is 1-20%, the temperature is 300-500 DEG C, the heating rate is ≤5 DEG C / min, and the holding time is 1-3 hours.
[0019] As a further preferred technical solution of the present application, the ruthenium salt solution is a ruthenium trichloride solution with a concentration of 5-20 mg / mL, and the mass ratio of the indium single-atom modified nitrogen-oxygen co-doped carbon carrier to the ruthenium trichloride is 1:0.25-0.5.
[0020] According to a third aspect of the present application, the present application provides a use of a Ru-based cluster hydro-oxidation electrocatalyst as a hydrogen conversion electrocatalytic material in a fuel cell.
[0021] Compared with the prior art, the present application can achieve the following beneficial effects:
[0022] (1) The catalyst synthesis method provided by the present application is simple, does not depend on specific synthesis equipment with high price and complex operation, and can be prepared on a large scale without complex steps, which is convenient to control and provides important technical support for promoting the commercialization of hydrogen energy and fuel cell catalysts.
[0023] (2) In the application, the electron of the ruthenium cluster is regulated by the indium single atom, so that the performance and the anti-poisoning of the fuel cell hydrogen oxidation reaction are significantly improved.
[0024] (3) The preparation of the catalyst in the application is based on a step-by-step wet chemical synthesis method. First, an indium single atom modified nitrogen doped carbon carrier (In1@CNO) is constructed, then the ruthenium cluster is loaded on the carrier through liquid immersion and subsequent reduction treatment, and finally the target catalyst is obtained. This method has the advantages of high universality, short reaction time, simple operation, etc. BRIEF DESCRIPTION OF DRAWINGS
[0025] The application will be further described in detail below in combination with the drawings and specific embodiments.
[0026] Figure 1 a in the figure is a TEM photo of the Ru AC / In1@CNO electrocatalyst prepared in Example 1 of the application; Figure 1 b in the figure is a HAADF-STEM photo, and the size distribution of Ru AC / In1@CNO; Figure 1 c in the figure is an aberration-corrected HAADF-STEM image.
[0027] Figure 2 is the XRD spectrum of the Ru AC / In1@CNO electrocatalyst prepared in Example 1 of the application.
[0028] Figure 3 a and b in the figure are the XPS spectra of Ru 3d and In 3d of the Ru AC / In1@CNO electrocatalyst prepared in Example 1 of the application.
[0029] Figure 4 a in the figure is the alkaline hydroxidation performance of the Ru AC / In1@CNO electrocatalyst prepared in Example 1 of the application, Figure 4 b in the figure is the anti-CO poisoning test of the Ru AC / In1@CNO electrocatalyst prepared in Example 1 of the application, wherein a commercial Pt / C catalyst is used as a control.
[0030] Figure 5 a in the figure is the alkaline hydroxidation performance of the Ru AC / In1@CNO electrocatalyst prepared in Example 2 of the application, Figure 5 b in the figure is the anti-CO poisoning test of the Ru AC / In1@CNO electrocatalyst prepared in Example 2 of the application, wherein a commercial Pt / C catalyst is used as a control.
[0031] Figure 6 a in the figure is the alkaline hydroxidation performance of the Ru NP / @CNO electrocatalyst prepared in Comparative Example 1 of the application, Figure 5The anti-CO poisoning test of the Ru NP / In1@CNO electrocatalyst prepared in Example 2 of the present application, wherein the Ru AC / In1@CNO electrocatalyst prepared in Example 1 and the commercial Pt / C catalyst were used as controls.
[0032] The purposes, functional features and advantages of the present application will be further illustrated in conjunction with the embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION
[0033] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely intended to illustrate and explain the present application, and are not intended to limit the present application.
[0034] Unless otherwise defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the present application belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; and the experimental methods, unless otherwise specified, are all conventional methods.
[0035] Example 1
[0036] 1. Preparation of In1@CNO with single-atom modified nitrogen and oxygen co-doped carbon support
[0037] (1) Preparation of precursor solution: 0.25 g of glucose and 5.0 g of dicyandiamide were accurately weighed and dissolved in 200 mL of deionized water together, and then magnetically stirred at room temperature for 30 minutes at a stirring rate of 550 r / min to obtain a clear solution. Then, 2 mL of an indium nitrate aqueous solution with a concentration of 0.0125 mol / L was slowly added dropwise under continuous stirring, and the stirring was continued for 2 hours after the dropwise addition was completed to ensure uniform mixing, thereby preparing a uniform precursor mixed solution.
[0038] (2) Precursor solidification: the above-mentioned precursor mixed solution was heated and stirred in an oil bath at 90°C, and evaporated and concentrated to a volume of about 50 mL. Then, the concentrated solution was quickly transferred and frozen with liquid nitrogen for 5 minutes, and then the completely frozen solid was placed in a freeze dryer and dried at -45°C for 24 hours to obtain a white sponge-like precursor powder.
[0039] (3) High-temperature pyrolysis: the dried white precursor powder was placed in a quartz boat and transferred to a tube furnace. Under an argon atmosphere with a flow rate of 50 mL / min, the temperature was programmed to rise to 900°C at a rate of 3°C / min, and pyrolysis was carried out at this temperature for 2 hours. After the pyrolysis was completed, the furnace was naturally cooled to room temperature, thereby obtaining a black In1@CNO with single-atom modified nitrogen and oxygen co-doped carbon support.
[0040] 2. Loading and activation of ruthenium clusters
[0041] (1) Impregnation loading: Accurately weigh 40 mg of the In1@CNO carrier prepared above, disperse it in 20 mL of ethanol, and sonicate it for 30 minutes to ensure complete dispersion. Under magnetic stirring, with the stirring rate controlled at 600 r / min, add 1.5 mL of ruthenium trichloride solution with a concentration of 10 mg / mL dropwise to the suspension. After the addition is complete, continue stirring at room temperature for 18 hours to complete the impregnation process.
[0042] (2) Drying and Reduction: The impregnated mixture was dried in a vacuum oven at 60°C for 12 hours to obtain a black powder. The powder was placed in a quartz boat and transferred to a tube furnace. Under a reducing atmosphere consisting of 10% H2 and 90% Ar (volume ratio), the temperature was programmed to rise to 400°C at a rate of 3°C / min and held at this temperature for 2 hours. After the reaction system was allowed to cool naturally to room temperature, the final catalyst product was obtained, denoted as Ru AC / In1@CNO, where the mass fraction of Ru was 10.42% and the mass fraction of In was 1.45%.
[0043] 3. Characterization of catalyst structure and morphology
[0044] The microstructure of the obtained Ru AC / In1@CNO catalyst was observed using transmission electron microscopy (TEM). Figure 1 As shown in image 'a', the catalyst exhibits an ultrathin, sheet-like structure. (High-power transmission electron microscopy (HRTEM) image) Figure 1 b) further demonstrates that ruthenium clusters with sizes of 1–3 nanometers are uniformly distributed on the support. High-angle annular dark-field scanning TEM (HAADF-STEM) image ( Figure 1 c) provides direct evidence for the coexistence of Ru atom clusters and isolated In single atoms on a carbon substrate. This ultra-small and uniform cluster structure facilitates the full exposure of active sites, thereby improving catalytic efficiency.
[0045] The crystal structure of the catalyst was characterized using X-ray diffraction (XRD), and the spectrum is shown below. Figure 2 As shown in the spectrum, no obvious crystallization diffraction peaks of metallic ruthenium were observed, indicating that the supported ruthenium species mainly exist in the form of extremely small, low-crystallinity clusters, which is consistent with the TEM observation results.
[0046] The electronic structure of the catalyst was characterized using X-ray photoelectron spectroscopy (XPS), and the spectrum is shown below. Figure 3 As shown in a and b in the spectrum. It is observed in the spectrum that the introduction of In increases the valence state of Ru, and Ru transfers electrons to In.
[0047] 4. Electrochemical performance testing
[0048] The hydrogen oxidation reaction (HOR) performance of the catalyst was evaluated using a standard three-electrode system on a CHI760E electrochemical workstation. The prepared Ru AC / In1@CNO catalyst was used as the working electrode, a platinum sheet was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. The working electrode was prepared as follows: 4 mg of the catalyst, 20 μL of a 5 wt% Nafion solution, and 980 μL of a mixed solvent of isopropanol / water (volume ratio 1:1) were ultrasonically dispersed together for 30 minutes to form a uniform slurry; then 10 μL of the slurry was dropped onto the surface of a rotating disc electrode and dried at room temperature for standby. Linear sweep voltammetry (LSV) tests were performed in a 1 M KOH electrolyte at a scan rate of 5 mV·s -1 .
[0049] Figure 4 The LSV curves of the Ru AC / In1@CNO catalyst of Example 1 and a commercial Pt / C (20%) catalyst are compared in a, which shows that the limiting current density of the Ru AC / In1@CNO is comparable to that of the commercial Pt / C, demonstrating its excellent hydrogen oxidation reaction catalytic activity. To evaluate the catalyst's resistance to poisoning, a 1000 ppm CO was introduced into the hydrogen for stability testing, and the results are shown in b of Figure 4 , which shows that the current density of the Ru AC / In1@CNO catalyst only decreases by about 13% after running in a CO-containing atmosphere for 5000 seconds, demonstrating excellent stability, while the commercial Pt / C catalyst is rapidly deactivated due to CO poisoning under the same conditions. The test results fully demonstrate that the Ru AC / In1@CNO catalyst prepared by the present application has both high catalytic activity and outstanding CO poisoning resistance.
[0050] Example 2: Adjusting the Ru content to a low loading compared to Example 1
[0051] 1. Preparation of In monatomic modification nitrogen and oxygen co-doped carbon carrier (In1@CNO)
[0052] (1) Preparation of the precursor solution: 0.25 g of glucose and 5.0 g of dicyandiamide were accurately weighed and dissolved in 200 mL of deionized water, and magnetically stirred at room temperature for 30 minutes at a stirring rate of 550 r / min. Then, 2 mL of an indium chloride aqueous solution with a concentration of 0.0125 mol / L was slowly added dropwise under continuous stirring, and the stirring was continued for 2 hours after the addition was completed to form a uniform mixed solution.
[0053] (2) Precursor solidification: The mixed solution was heated and stirred in a 90 °C oil bath, and concentrated by evaporation to a volume of about 50 mL. Subsequently, the concentrated solution was quickly transferred and frozen with liquid nitrogen for 5 minutes. The completely frozen solid was placed in a freeze dryer and dried at -45 °C for 24 hours to obtain a white sponge-like precursor powder.
[0054] (3) The dried white precursor powder was placed in a quartz boat and transferred to a tube furnace. Under an argon atmosphere with a flow rate of 50 mL / min, the temperature was programmed to rise to 900 °C at a rate of 3 °C / min, and maintained at this temperature for 2 hours. After the pyrolysis was completed, the furnace was naturally cooled to room temperature to obtain a black indium single-atom modified nitrogen-doped carbon carrier, denoted as In1@CNO.
[0055] 2. Loading and activation of ruthenium clusters
[0056] (1) Impregnation loading: 40 mg of the In1@CNO carrier prepared above was accurately weighed and dispersed in 20 mL of ethanol, and ultrasonically treated for 30 minutes. Under magnetic stirring, 1 mL of ruthenium trichloride solution with a concentration of 10 mg / mL was added dropwise to the suspension, and after the addition was completed, stirring was continued at room temperature for 18 hours, with a stirring rate controlled at 550 r / min.
[0057] (2) Drying and reduction: The impregnated mixture was dried in a vacuum oven at 60 °C for 12 hours to obtain a black powder. The powder was placed in a quartz boat and transferred to a tube furnace. Under a reducing atmosphere composed of 10% H2 and 90% Ar (volume ratio), the temperature was programmed to rise to 500 °C at a rate of 3 °C / min, and maintained at this temperature for 2 hours. After the reaction system was naturally cooled to room temperature, the catalyst product was obtained. The mass fraction of Ru was 7.01%, and the mass fraction of In was 1.32%.
[0058] 3. Catalyst structure and morphology characterization
[0059] The structure and morphology of this sample were consistent with those of the catalyst samples obtained in the examples.
[0060] 4. Electrochemical performance test
[0061] The hydrogen oxidation reaction (HOR) performance of the catalyst was evaluated using a standard three-electrode system on a CHI760E electrochemical workstation. The prepared Ru AC / In1@CNO catalyst was used as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The working electrode was prepared as follows: 4 mg of catalyst, 2 μL of 5 wt% Nafion solution, and 980 μL of a mixed solvent of isopropanol / water (volume ratio 1:1) were ultrasonically dispersed together for 30 minutes to form a uniform slurry; then 10 μL of the slurry was dropped onto the surface of a rotating disc electrode and dried at room temperature for standby use. Linear sweep voltammetry (LSV) tests were carried out in 1 M KOH electrolyte with a scan rate of 5 mV·s -1 .
[0062] Figure 5 The LSV curves of the Ru AC / In1@CNO catalyst of Example 2 and the commercial Pt / C (20%) catalyst are shown in a of FIG. 8. It can be seen that the limiting current density of Ru AC / In1@CNO is comparable to that of commercial Pt / C at low potential, demonstrating its excellent hydrogen oxidation reaction catalytic activity. To evaluate the catalyst's resistance to poisoning, a 1000 ppm CO was introduced into the hydrogen gas for stability testing, and the results are shown in b of FIG. 8. It can be seen that the current density of the Ru AC / In1@CNO catalyst of Example 2 only decays by about 20.1% after running in a CO-containing atmosphere for 3000 seconds, showing excellent stability. Figure 5
[0063] Example 3: Scale-up preparation compared to Example 1
[0064] 1. Preparation of indium monatomic modified nitrogen and oxygen co-doped carbon support (In1@CNO)
[0065] (1) Preparation of precursor solution: 5.0 g of glucose and 100 g of dicyandiamide were accurately weighed and dissolved in 4 L of deionized water, and magnetically stirred at room temperature for 60 minutes. Then, 40 mL of 0.0125 mol / L indium nitrate aqueous solution was slowly added dropwise under continuous stirring, and the stirring was continued for 2 hours after the addition was completed to ensure the formation of a uniform mixed solution.
[0066] (2) Precursor solidification: the above mixed solution was heated and stirred in a 90°C oil bath, and evaporated and concentrated to a volume of about 1 L. Then, the concentrated solution was quickly transferred and deeply frozen with liquid nitrogen. The completely frozen solid was placed in a freeze dryer and dried at -45°C for 48 hours to obtain a white sponge-like solid precursor.
[0067] (3) High-temperature pyrolysis: The dried solid precursor was placed in a large quartz boat and transferred to a tube furnace. Under the argon atmosphere with a flow rate of 50 mL / min, the temperature was programmed to rise to 900 °C at a rate of 3 °C / min and kept at this temperature for 2 h. After the pyrolysis, the furnace was naturally cooled to room temperature, and a black In single-atom decorated nitrogen-doped carbon support was obtained, denoted as In1@CNO.
[0068] 2. Loading and activation of ruthenium clusters
[0069] (1) Impregnation loading: 1.0 g of the In1@CNO support prepared above was accurately weighed and dispersed in 500 mL of ethanol, and ultrasonically treated for 30 min to ensure full dispersion. Under strong mechanical stirring, 37.5 mL of a ruthenium trichloride solution with a concentration of 10 mg / mL was added dropwise to the suspension, and after the addition was completed, the stirring was continued at room temperature for 18 h to ensure full impregnation.
[0070] (2) Drying and reduction: The impregnated mixture was dried in a vacuum oven at 60 °C for 12 h to obtain a black powder. The powder was placed in a large quartz boat and transferred to a tube furnace. Under a reducing atmosphere composed of 10% H2and 90% Ar (volume ratio), the temperature was programmed to rise to 500 °C at a rate of 3 °C / min and kept at this temperature for 2 h. After the reaction system was naturally cooled to room temperature, the catalyst product prepared on a large scale was obtained, denoted as Ru AC / In1@CNO.
[0071] It was found by experiment that the structure and morphology of the batch sample were consistent with those of the catalyst of Example 1; the current density reached 2.40 mA / cm 2 under a 50 mV overpotential, and it could stably operate for 3600 s under 1000 ppm CO, indicating that it still maintained high catalytic activity and CO resistance after being prepared on a large scale.
[0072] Comparative Example 1
[0073] As a comparative experiment of Example 1, the only difference was that the preparation of the “In single-atom decorated nitrogen-oxygen co-doped carbon support (In1@CNO)” process omitted the indium chloride aqueous solution, and the remaining steps were the same as those of Example 1. Finally, a catalyst product prepared from a CNO carbon support without In single-atom decoration was obtained, denoted as Ru NP@CNO, wherein the mass fraction of Ru was 10.80% and the mass fraction of In was 0%.
[0074] It was found by experiment that although the structure and morphology of the sample obtained in the comparative example were consistent with those of the catalyst sample of Example 1, its catalytic performance was much worse than that of Example 1, as indicated by the current density under a 50 mV overpotential, as shown in a of Figure 6 ; and the stable operation test was as shown in Figure 6b in the figure shows that the catalyst is almost completely deactivated after running 2500 s under 1000 ppm CO, which is comparable to the performance of commercial Pt / C (20%) catalyst. It is suggested that the introduction of In enhances the catalytic activity and CO tolerance of Ru cluster.
[0075] Although the above describes the specific embodiments of the present application, those skilled in the art should understand that these are only illustrative, and various changes or modifications can be made to the embodiments without departing from the principles and essence of the present application, and the protection scope of the present application is only defined by the appended claims.
Claims
1. A method for preparing a ruthenium group cluster electrocatalyst for resisting CO poisoning, characterized in that, Includes the following steps: S1. Glucose, dicyandiamine and indium salt are mixed in a solvent, concentrated by evaporation, and then subjected to freezing and freeze-drying to obtain a solid precursor. S2. Under an inert atmosphere, the solid precursor was calcined at 800~1100℃ for the first time to obtain an indium single-atom modified nitrogen-oxygen co-doped carbon support. S3. The nitrogen-oxygen co-doped carbon support modified with indium single atoms is dispersed in a solvent and impregnated with ruthenium salt solution to achieve ruthenium cluster loading. The resulting loaded product is dried and then calcined a second time at 300~500℃ under a reducing atmosphere to obtain an ultrathin sheet-like ruthenium group cluster hydroxide electrocatalyst.
2. The preparation method of the ruthenium group cluster electrocatalyst for CO poisoning resistance according to claim 1, characterized in that, The indium salt is selected from indium nitrate or indium chloride.
3. The preparation method of the ruthenium group cluster electrocatalyst for CO poisoning resistance according to claim 1, characterized in that, The mass ratio of glucose, dicyandiamine, and indium salt is 1:20:0.0095~0.
057.
4. The preparation method of the ruthenium group cluster electrocatalyst for CO poisoning resistance according to claim 1, characterized in that, The temperature of the first calcination is 800~1100℃, the heating rate is ≤5℃ / min, and the holding time is 1~3 hours.
5. The preparation method of the ruthenium group cluster electrocatalyst for CO poisoning resistance according to claim 1, characterized in that, The soaking time is 12 to 36 hours.
6. The preparation method of the ruthenium group cluster electrocatalyst for CO poisoning resistance according to claim 1, characterized in that, The second calcination is carried out in an atmosphere of H2 and Ar, with H2 accounting for 1~20% of the volume, a temperature of 300~500℃, a heating rate of ≤5℃ / min, and a holding time of 1~3 hours.
7. The preparation method of the ruthenium group cluster electrocatalyst for CO poisoning resistance according to claim 1, characterized in that, The ruthenium salt solution is a ruthenium trichloride solution with a concentration of 5~20 mg / mL, and the mass ratio of the indium single-atom modified nitrogen-oxygen co-doped carbon support to ruthenium trichloride is 1:0.25~0.
5.
8. A ruthenium group cluster electrocatalyst for hydroxide oxidation, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.
9. The ruthenium group cluster electrocatalyst for hydroxide oxidation according to claim 8, characterized in that, The ruthenium cluster hydroxide electrocatalyst has an ultrathin sheet structure, with indium single-atom modified nitrogen-oxygen co-doped carbon material as the support, and ruthenium clusters as active centers loaded on the support; wherein, based on the total mass of the catalyst, the loading amount of indium single atoms is 0.5~3 wt%, the loading amount of ruthenium clusters is 5~15 wt%, and the average particle size of the ruthenium clusters is 1~3 nm.
10. The application of the ruthenium group cluster hydroxide electrocatalyst according to claim 8 or 9 in fuel cells.