A method for loading zinc clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds and its application
By loading sub-nanometer zinc atom clusters onto the surface of ruthenium nanoparticles and using H2 thermally driven melting to break the Zn-N bonds, the problem of excessive adsorption of hydrogen intermediates and hydroxide species in ruthenium-based catalysts was solved, improving the activity and stability of the catalyst and providing an efficient electrocatalytic hydrogen evolution pathway.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- TAIYUAN UNIVERSITY OF TECHNOLOGY
- Filing Date
- 2025-12-26
- Publication Date
- 2026-05-29
AI Technical Summary
Existing ruthenium-based catalysts exhibit excessive adsorption of hydrogen intermediates and hydroxide species in the electrocatalytic hydrogen evolution reaction, leading to difficulties in desorption and poisoning and deactivation of active sites. Traditional methods struggle to synergistically address these two issues.
A method using H2 thermally driven melting of Zn-N bonds was employed to load sub-nanometer-scale zinc atom clusters onto the surface of ruthenium nanoparticles. Through an indirect hydrogenation pyrolysis strategy, hydrogen was used to induce the pyrolysis of the Zn-N4/Ru cluster structure, releasing and confining zinc atoms to nucleate and grow into sub-nanometer-scale atom clusters on the surface of ruthenium nanoparticles.
The catalytic activity and stability of ruthenium-based catalysts were improved, the hydrogen adsorption energy was optimized, the adsorption of hydroxide ions was weakened, and the efficiency and stability of electrocatalytic hydrogen evolution reaction were enhanced.
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Figure CN122105480A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of nanocatalytic material preparation technology, specifically relating to a method and its application for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds. Background Technology
[0002] Ruthenium-based catalysts have shown great potential in electrocatalytic hydrogen evolution reactions due to their relatively low cost and suitable adsorption strength for hydrogen intermediates. However, the excessive adsorption of hydrogen intermediates and hydroxide species by Ru leads to difficulties in hydrogen desorption and poisoning and deactivation of active sites. In recent years, constructing strong metal-support interactions or preparing alloys to modulate the electronic structure of ruthenium has become a common strategy. However, these methods are often complex and have limited modulating effects, making it difficult to achieve a synergistic solution to the two problems mentioned above.
[0003] It is worth noting that zinc, due to its unique electronic structure, is considered to have a natural "repulsive" effect on hydrogen species. Introducing zinc into the local environment of ruthenium could theoretically effectively optimize the adsorption energy of ruthenium for hydrogen. Simultaneously, theoretical calculations indicate that the introduction of zinc can also moderately upregulate the d-band center of ruthenium, thereby weakening its adsorption of oxygen-containing species such as hydroxide ions, potentially alleviating the OH- ionization problem. - The issue of poisoning remains. However, combining zinc with ruthenium in an ideal structural form that fully utilizes its electronic regulation without completely covering or shielding the active sites of ruthenium presents a significant challenge. Traditional alloying or simple physical mixing methods struggle to achieve such precise interface construction at the atomic scale. Therefore, there is an urgent need to develop novel material design strategies and controllable preparation methods to create a new type of ruthenium-based catalytic material capable of synergistically achieving both hydrogen desorption promotion and hydroxide poisoning resistance. Summary of the Invention
[0004] The purpose of this invention is to provide a method and its application for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds.
[0005] The present invention adopts the following technical solution: A method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds utilizes an indirect hydrogenation pyrolysis strategy to cover the surface of Ru nanoparticles loaded on nitrogen-doped carbon supports with a layer of sub-nanometer-scale zinc atom clusters.
[0006] Furthermore, the indirect hydrogenation cracking strategy refers to the selective pyrolysis of the dual-confined Zn-N4 / Ru cluster structure induced by H2 atmosphere, in which the released Zn atoms are confined on the surface of Ru nanoparticles and nucleate and grow into sub-nanometer-scale atomic clusters.
[0007] A method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds includes the following steps: S1. Synthesis of ZIF-8: Dimethylimidazole was dispersed in methanol to obtain solution A, and zinc nitrate hexahydrate was dispersed in methanol to obtain solution B. Solution A and solution B were mixed and stirred at 35°C for 4 hours. The product was collected by centrifugation, washed several times with methanol and ethanol respectively, and then dried at 60°C overnight to obtain sample ZIF-8. S2. Synthesis of Zn single atoms / NC: The fully ground ZIF-8 powder was annealed at 1000℃ for 3h in a mixed atmosphere of H2 and Ar to obtain nitrogen-doped MOF-derived carbon microporous-vacancy framework. S3. Synthesis of Ru nanoclusters-Zn single atoms / NC: Add ruthenium trichloride aqueous solution to deionized water containing Zn single atoms / NC, heat in a water bath at 60°C for 16 hours, wash three times with deionized water after heating, and dry overnight to obtain the precursor; Synthesis of S4, Ru nanoparticle-supported Zn clusters / NC: The precursor was heated to 800℃ for 2h in a mixed atmosphere of H2 and Ar to obtain a black solid powder, namely Ru nanoparticle-supported Zn clusters / NC.
[0008] Furthermore, in S1, the ratio of dimethylimidazole to methanol is 50-150 mmol: 30-90 mL, and the ratio of zinc nitrate hexahydrate to methanol is 20-40 mmol: 180-540 mL.
[0009] Furthermore, in S2, the heating rate is 2-10℃ / min, the volume content of H2 in the mixed atmosphere of H2 and Ar is 5%, and the flow rate of the mixed atmosphere is 60-200mL / min.
[0010] Furthermore, in S3, the concentration of ruthenium trichloride aqueous solution is 0.04 g / mL; the ratio of ruthenium trichloride aqueous solution, Zn single atom / NC, and deionized water is 100-800 µL: 25 mg: 10 mL.
[0011] Furthermore, in S4, the volume content of H2 in the mixed atmosphere of H2 and Ar is 2%-30%, and the heating rate is 2-10℃ / min.
[0012] The zinc cluster catalyst supported on the surface of ruthenium nanoparticles prepared according to the above method was used for hydrogen evolution reaction.
[0013] This invention involves the pyrolysis of coordinated-spatial-confined Ru nanoclusters-Zn single-atom / NC precursors. H2 serves as the key inducing agent, utilizing the active hydrogen species generated from the catalytic cracking of hydrogen gas at ruthenium sites. Through the hydrogen spillover effect, the thermodynamically stable Zn-N bonds are broken, activating and facilitating the migration of Zn atoms. These highly mobile Zn atoms are captured on the surface of pre-formed Ru nanoparticles, confined to the Ru surface and assembled into Zn atom clusters due to strong metal-metal interactions. The prepared material exhibits excellent electrocatalytic hydrogen evolution activity, providing a research foundation and a universal construction strategy for the design of heteronuclear metal cluster catalysts supported on metal nanoparticles.
[0014] The beneficial effects of this invention are as follows: This invention discloses a method and its application for loading zinc clusters onto the surface of ruthenium nanoparticles based on H2-driven thermal cleavage of Zn-N bonds. First, a zinc-containing metal-organic framework material is pyrolyzed to generate nitrogen-containing porous cavities and a small amount of zinc. Then, through nitrogen coordination and narrow-pore confinement of Ru clusters inherited from the precursor, the active hydrogen species generated by the catalytic cracking of hydrogen gas at ruthenium sites are utilized. Through the hydrogen spillover effect, the thermodynamically stable Zn-N bonds are broken, and the released Zn atoms are confined on the surface of Ru nanoparticles and nucleate and grow into sub-nanometer-scale clusters. This invention improves the intrinsic catalytic activity and stability of Ru-based catalysts by loading heteronuclear sub-nanometer-scale Zn metal clusters onto Ru metal nanoparticles, providing a new pathway for efficient energy conversion. Attached Figure Description
[0015] Figure 1 TEM image of a single Zn atom / NC; Figure 2 The image shows a HAADF-STEM image of Ru nanoclusters-Zn single atoms / NC in Example 1. Figure 3 The image shows a HAADF-STEM image of Ru nanoparticles loaded with Zn atom clusters / NC in Example 1. Figure 4 The image shows a HAADF-STEM image of Ru nanoparticles loaded with Zn single atoms / NC in Example 1. Figure 5 The electrocatalytic HER performance of Ru nanoparticles loaded with Zn atom clusters / NC in Example 1 and Ru nanoparticles loaded with Zn single atoms / NC in Comparative Example 1 in 1 M KOH solution; Figure 6 The performance of the Ru nanoparticle-supported Zn cluster / NC catalyst prepared in Example 1 in the AEMWEs device; Figure 7 This is a TEM image of Ru nanoparticles loaded with Zn atom clusters / NC in Example 2; Figure 8 This is a TEM image of Ru nanoparticles loaded with Zn atom clusters / NC in Example 3; Figure 9 The electrocatalytic HER performance of Ru nanoparticles loaded with Zn clusters / NC in 1 M KOH solution is shown in Examples 2 and 3. Detailed Implementation
[0016] The following embodiments are merely preferred technical solutions of the present invention and are not intended to limit the present invention in any way. For those skilled in the art, the present invention can have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
[0017] Example 1 A method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, the specific steps of which are as follows: S1. Synthesis of ZIF-8: 86.4 mmol of dimethylimidazole was dispersed in 36 mL of methanol to obtain solution A, and 21.6 mmol of zinc nitrate hexahydrate was dispersed in 216 mL of methanol to obtain solution B. Solution A and solution B were mixed and stirred at 35 °C for 4 h. The product was collected by centrifugation, washed 5 times with methanol and ethanol respectively, and then dried at 60 °C overnight to obtain sample ZIF-8. S2. Synthesis of Zn single atoms / NC: Thoroughly ground ZIF-8 powder was annealed at 1000℃ for 3 hours in a mixed atmosphere of H2 and Ar, with a heating rate of 2℃ / min and a gas flow rate of 150mL / min, to obtain a nitrogen-doped MOF-derived carbon microporous-vacancy framework. Since Zn has a boiling point of 907℃, pyrolysis of ZIF-8 at 1000℃ will lead to the volatilization of some Zn atoms.
[0018] Figure 1 The TEM image shows a single Zn atom / NC structure, revealing that the rhombic dodecahedral morphology of the ZIF-8 precursor is well preserved and no nanoparticles are observed. This indicates that the volatilization of Zn atoms in ZIF-8 did not cause structural damage, and that the retained Zn is dispersed in single-atom form within nitrogen-doped carbon.
[0019] S3. Synthesis of Ru nanoclusters-Zn single atoms / NC: 375 μL of ruthenium trichloride aqueous solution (0.04 g / mL) was added to deionized water containing Zn single atoms / NC, and heated in a water bath at 60 °C for 16 h. After heating, the product was washed three times with deionized water and dried overnight to obtain the precursor.
[0020] Figure 2The HAADF-STEM image of Ru nanoclusters-Zn single atoms / NC shows the presence of confined bimetallic sites, with Ru and Zn existing as single atoms or small nanoclusters, respectively.
[0021] Synthesis of S4, Ru nanoparticle-supported Zn clusters / NC: The precursor was heated at 800℃ for 2h in a mixed atmosphere of H2 and Ar at a heating rate of 2℃ / min and a gas flow rate of 150mL / min to obtain a black solid powder, namely Ru nanoparticle-supported Zn clusters / NC. Figure 3 The image shows a HAADF-STEM image of Ru nanoparticles loaded with Zn clusters / NC. In the left image, the surface of the Ru nanoparticles can be seen to be covered by a layer of sub-nanometer Zn clusters. In the right image, the atomic intensity distribution shows that several atoms are in a high intensity state, which further confirms the presence of Ru clusters on the surface.
[0022] Comparative Example 1 Synthesis of Ru nanoparticles loaded with Zn single atoms / NC An appropriate amount of Ru nanoclusters-Zn single-atom / NC precursor, identical to that in Example 1, was heat-treated under a pure Ar atmosphere. The resulting sample was designated as Ru nanoparticle-supported Zn single-atom / NC. Figure 4 HAADF-STEM images of Ru nanoparticles loaded with Zn single atoms / NC. It can be seen that, compared to materials treated with H2, only individually dispersed Zn single atoms exist on the surface of Ru nanoparticles. This evidence suggests that simple pyrolysis has a weak effect on the fragmentation of Zn-N sites, while the presence of H2 enhances the attack on Zn-N sites and never induces the formation of Zn atom clusters on the surface of Ru nanoparticles.
[0023] Figure 5 For the electrocatalytic HER performance testing of Example 1 and Comparative Example 1 in 1 M KOH solution, the catalyst was coated on carbon paper (2 mg cm⁻¹). -2 The LSV test was performed using a three-electrode system with Hg / HgO (alkaline medium) as the working electrode, Hg / HgO (alkaline medium) as the reference electrode, and a graphite rod as the counter electrode. The LSV test range was -0.85 to -1.2 V vs. Hg / HgO (0.075 to -1.2 V vs. Hg / HgO), and the scan rate was 50 mV s. -1 The Tafel slope was determined by plotting the logarithm of the current density versus the overpotential (log |j|). Example 1 material (Ru nanoparticles supporting Zn clusters / NC) at 100 mA cm⁻¹ -2The overpotential at the current density was 56 mV, significantly lower than the 106 mV and 114 mV of the material in Comparative Example 1 (Ru nanoparticles supporting Zn single atoms / NC) and 20% Pt / C, respectively. The Tafel slope of Example 1 was 16.43 mV dec. -1 It also significantly outperformed Comparative Example 1 and 20% Pt / C, demonstrating its superior catalytic activity and reaction kinetics.
[0024] Figure 6 The performance of the catalyst material prepared in Example 1 in an AEMWEs device is shown. AEM water electrolysis for hydrogen production refers to the process of producing hydrogen using an anion exchange membrane as the solid electrolyte and 1M KOH as the raw material for water electrolysis. In short, it uses electrical energy to decompose water molecules into hydrogen and oxygen. This process is completed with the assistance of an ion exchange membrane; hydrogen is generated on one side of the membrane, and oxygen is generated on the other, achieving precise control of water electrolysis. This material is used for the hydrogen evolution reaction in alkaline electrochemical water decomposition. The lower the voltage required to reach a certain current density, the better the hydrogen evolution performance of the material. As shown in the figure, at 70 °C, the material only requires 1.82 V to reach 1 A cm⁻¹. -2 The 20% Pt / C content indicates that this material has certain application potential at a near-industrial scale.
[0025] Example 2 A method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, the specific steps of which are as follows: S1. Synthesis of ZIF-8: 86.4 mmol of dimethylimidazole was dispersed in 36 mL of methanol to obtain solution A. 21.6 mmol of zinc nitrate hexahydrate was dispersed in 216 mL of methanol to obtain solution B. Solution A and solution B were mixed and stirred at 35 °C for 4 h. The product was collected by centrifugation, washed 5 times with methanol and ethanol respectively, and then dried at 60 °C overnight to obtain sample ZIF-8.
[0026] S2. Synthesis of Zn single atoms / NC: Thoroughly ground ZIF-8 powder was annealed at 1000℃ for 3 h in a mixed atmosphere of H2 and Ar, with a heating rate of 2℃ / min and a gas flow rate of 150 mL / min, to obtain a nitrogen-doped MOF-derived carbon microporous-vacancy framework. Since Zn has a boiling point of 907℃, pyrolysis of ZIF-8 at 1000℃ will lead to the volatilization of some Zn atoms.
[0027] S3. Synthesis of Ru nanoclusters-Zn single atoms / NC: 125 μL of ruthenium trichloride aqueous solution (0.04 g / mL) was added to deionized water containing Zn single atoms / NC, and heated in a water bath at 60℃ for 16 h. After heating, the product was washed three times with deionized water and dried overnight to obtain the precursor.
[0028] Synthesis of S4, Ru nanoparticle-supported Zn clusters / NC: The precursor was heated at 800 °C for 2 h in a mixed atmosphere of H2 and Ar at a heating rate of 2 °C / min and a gas flow rate of 150 mL / min to obtain a black solid powder, namely Ru nanoparticle-supported Zn clusters / NC.
[0029] Example 3 A method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, the specific steps of which are as follows: S1. Synthesis of ZIF-8: 86.4 mmol of dimethylimidazole was dispersed in 36 mL of methanol to obtain solution A. 21.6 mmol of zinc nitrate hexahydrate was dispersed in 216 mL of methanol to obtain solution B. Solution A and solution B were mixed and stirred at 35 °C for 4 h. The product was collected by centrifugation, washed 5 times with methanol and ethanol respectively, and then dried at 60 °C overnight to obtain sample ZIF-8.
[0030] S2. Synthesis of Zn single atoms / NC: Thoroughly ground ZIF-8 powder was annealed at 1000℃ for 3 h in a mixed atmosphere of H2 and Ar, with a heating rate of 2℃ / min and a gas flow rate of 150 mL / min, to obtain a nitrogen-doped MOF-derived carbon microporous-vacancy framework. Since the boiling point of Zn is 907℃, pyrolysis of ZIF-8 at 1000℃ will lead to the volatilization of some Zn atoms.
[0031] S3. Synthesis of Ru nanoclusters-Zn single atoms / NC: 625 μL of ruthenium trichloride aqueous solution (0.04 g / mL) was added to deionized water containing Zn single atoms / NC, and heated in a water bath at 60 °C for 16 h. After heating, the product was washed three times with deionized water and dried overnight to obtain the precursor.
[0032] Synthesis of S4, Ru nanoparticle-supported Zn clusters / NC: The precursor was heated at 800℃ for 2h in a mixed atmosphere of H2 and Ar at a heating rate of 2℃ / min and a gas flow rate of 150 mL / min to obtain a black solid powder, namely Ru nanoparticle-supported Zn clusters / NC.
[0033] Figure 7 and Figure 8The images shown are TEM images of Ru nanoparticles loaded with Zn atom clusters / NC in Examples 2 and 3, respectively. It can be seen that the size of the Ru nanoparticles increases with increasing Ru loading. Furthermore, from... Figure 9 As can be seen from the data, Examples 2 and 3 were performed at 100 mAcm. -2 The overpotentials at the current densities were 105 mV and 94 mV, respectively, both lower than those of the Ru nanoparticle-supported Zn atom clusters / NC in Example 1. This indicates that the catalytic performance changes with the size and coverage of the atom clusters, demonstrating the tunability of the method.
[0034] Based on the above test results, it can be seen that the Ru nanoparticle-supported Zn cluster / NC catalyst constructed in this invention exhibits excellent electrocatalytic HER activity and stability under alkaline conditions. This catalyst combines zinc with ruthenium in an ideal structural form that fully utilizes its electronic regulation function without completely covering or shielding the ruthenium active sites, effectively solving the problem of excessive adsorption of hydrogen intermediates and hydroxide species present in ruthenium-based catalysts. In summary, this study developed a highly efficient and stable Ru nanoparticle-supported Zn cluster / NC catalyst, providing an effective approach to improving the efficiency of electrocatalytic HER and showing potential application prospects.
[0035] This invention addresses the problem of excessive adsorption of hydrogen intermediates and hydroxide species in existing ruthenium-based catalysts by providing an H2-assisted confined pyrolysis strategy to controllably assemble sub-nanometer-scale Zn atom clusters on the surface of Ru nanoparticles. Compared with existing technologies, the pyrolysis of coordinated-spatial confined Ru nanoclusters-Zn single-atom / NC precursors utilizes the active hydrogen species generated from the catalytic cracking of hydrogen at ruthenium sites. Through the hydrogen spillover effect, the thermodynamically stable Zn-N bonds are broken, enabling Zn atoms to "activate" and migrate. These highly mobile Zn atoms are captured by the pre-formed Ru nanoparticle surface and, due to strong metal-metal interactions, are confined on the Ru surface and assembled into Zn atom clusters. The prepared material modulates the intrinsic catalytic activity of the Ru-based catalyst. This innovative design provides a research foundation and a universal construction strategy for the development of heteronuclear metal cluster catalysts supported on metal nanoparticles.
[0036] The above embodiments are only used to illustrate the content of the present invention, but they are not intended to limit the present invention. Those skilled in the art can make corresponding adjustments and modifications without departing from the scope of the present invention. Therefore, all technical solutions formed by equivalent substitutions or equivalent modifications are within the protection scope of the present invention.
Claims
1. A method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, characterized in that: The method utilizes an indirect hydrogenation pyrolysis strategy, which allows the surface of Ru nanoparticles loaded on a nitrogen-doped carbon support to be covered with a layer of sub-nanometer-scale zinc atom clusters.
2. The method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, as described in claim 1, is characterized in that: The indirect hydrogenation pyrolysis strategy refers to the selective pyrolysis of the double-confined Zn-N4 / Ru cluster structure induced by H2 atmosphere, in which the released Zn atoms are confined on the surface of Ru nanoparticles and nucleate and grow into sub-nanometer-scale atomic clusters.
3. The method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, as described in claim 1, is characterized in that: Includes the following steps: S1. Synthesis of ZIF-8: Dimethylimidazole was dispersed in methanol to obtain solution A, and zinc nitrate hexahydrate was dispersed in methanol to obtain solution B. Solution A and solution B were mixed and stirred at 35°C for 4 hours. The product was collected by centrifugation, washed several times with methanol and ethanol respectively, and then dried at 60°C overnight to obtain sample ZIF-8. S2. Synthesis of Zn single atoms / NC: The fully ground ZIF-8 powder was annealed at 1000℃ for 3h in a mixed atmosphere of H2 and Ar to obtain nitrogen-doped MOF-derived carbon microporous-vacancy framework. S3. Synthesis of Ru nanoclusters-Zn single atoms / NC: Add ruthenium trichloride aqueous solution to deionized water containing Zn single atoms / NC, heat in a water bath at 60°C for 16 hours, wash three times with deionized water after heating, and dry overnight to obtain the precursor; Synthesis of S4, Ru nanoparticle-supported Zn clusters / NC: The precursor was heated to 800℃ for 2h in a mixed atmosphere of H2 and Ar to obtain a black solid powder, namely Ru nanoparticle-supported Zn clusters / NC.
4. The method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, as described in claim 3, is characterized in that: In S1, the ratio of dimethylimidazole to methanol is 50-150 mmol: 30-90 mL, and the ratio of zinc nitrate hexahydrate to methanol is 20-40 mmol: 180-540 mL.
5. The method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, as described in claim 3, is characterized in that: In S2, the heating rate is 2-10℃ / min, the volume content of H2 in the mixed atmosphere of H2 and Ar is 5%, and the flow rate of the mixed atmosphere is 60-200mL / min.
6. The method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, as described in claim 4, is characterized in that: In S3, the concentration of ruthenium trichloride aqueous solution is 0.04 g / mL; the ratio of ruthenium trichloride aqueous solution, Zn single atom / NC, and deionized water is 100-800 µL: 25 mg: 10 mL.
7. The method for loading zinc atom clusters on the surface of ruthenium nanoparticles based on H2 thermally driven melting of Zn-N bonds, as described in claim 4, is characterized in that: In S4, the volume content of H2 in the mixed atmosphere of H2 and Ar is 2%-30%, and the heating rate is 2-10℃ / min.
8. A zinc cluster catalyst supported on the surface of ruthenium nanoparticles prepared by the preparation method of claim 4 for use in hydrogen evolution reaction.