Preparation and application of Ru@cl-c catalyst

Abstract

This invention provides a method for preparing and applying a Ru@Cl-C catalyst. First, poplar wood and PVC are mixed and co-pyrolyzed to obtain a chlorine-doped carbon precursor. Then, an alkali activation treatment is used to further optimize the specific surface area, pore distribution, and surface active sites of the carbon support. After washing and drying, a chlorine-doped activated carbon support is obtained. Finally, a ruthenium source precursor is mixed with the activated Cl-C support, and a hydrothermal calcination process is used to achieve uniform loading of the ruthenium active component. Subsequent post-treatment yields the Ru@Cl-C catalyst. When the prepared Ru@Cl-C catalyst is applied to the electrolysis of water to produce hydrogen, it can fully utilize the electronic regulation effect of Cl doping and the catalytic performance of the Ru active component, significantly improving the reaction efficiency. This invention features a rationally designed and environmentally friendly preparation process, providing a practical technical solution for the preparation of highly efficient water electrolysis catalysts for hydrogen production.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalysts, specifically relating to the preparation and application of a Ru@Cl-C catalyst. Background Technology

[0002] Green hydrogen is a clean secondary energy source with zero carbon emissions, and water electrolysis is currently the green hydrogen production technology with the greatest potential for large-scale development. A current challenge is the sluggish kinetics of the hydrogen evolution reaction (HER) at the cathode during water electrolysis, requiring highly efficient electrocatalysts to reduce the reaction overpotential and improve reaction efficiency. Therefore, developing high-performance, low-cost HER electrocatalysts is crucial for promoting the practical application of water electrolysis technology.

[0003] Currently, platinum (Pt)-based catalysts are the best-performing catalysts for HER (hydrogen ion exchange), but the scarcity and high cost of platinum severely restrict their large-scale application. Ruthenium (Ru) has become an ideal alternative to Pt-based catalysts due to its hydrogen adsorption free energy being close to that of platinum and its significantly lower cost, but its intrinsic activity still needs to be improved.

[0004] The performance of carbon supports has a decisive influence on the activity of Ru-based catalysts. An ideal carbon support needs to possess high specific surface area, abundant pore structure, good electrical conductivity, and strong metal-support interaction. Traditional fossil-based carbon supports are non-renewable and have limited tunability of surface chemical properties, making it difficult to achieve efficient dispersion and electronic structure control of Ru nanoparticles.

[0005] Biomass-derived carbon supports have become a research hotspot due to their advantages such as renewable raw materials, low cost, and tunable structure. Poplar wood, as an abundant source of lignocellulose biomass, has a high carbon content and wide availability. Furthermore, the oxygen-containing functional groups in its structure can promote the formation of porous structures and the anchoring of metal particles, making it an excellent precursor for carbon support preparation. Meanwhile, the large-scale accumulation of waste polyvinyl chloride (PVC) causes severe environmental pressure. Its chlorine-containing properties allow for in-situ halogen doping, which can effectively regulate the defect density of carbon supports, remove oxygen-containing functional groups, strengthen metal-support interactions, and improve catalyst performance.

[0006] In existing technologies, biomass carbon supports are mostly prepared using single raw materials, lacking effective halogen doping strategies, and exhibiting poor Ru loading dispersion. Furthermore, the resource utilization of waste PVC is not closely integrated with the functional modification of biomass carbon supports, failing to achieve synergy between high-value raw material utilization and catalyst performance improvement. Therefore, developing a technology that uses poplar wood as a biomass precursor and waste PVC as a halogen source to prepare a high-performance Ru-based hydrogen evolution catalyst through a simple process can not only solve the problem of waste plastic pollution but also reduce catalyst costs and improve catalytic performance, possessing significant economic and environmental value. Summary of the Invention

[0007] Purpose of the invention: The purpose of this invention is to provide a method for preparing Ru@Cl-C water electrolysis hydrogen production catalyst to solve the problems of high cost and low activity of traditional catalysts.

[0008] Technical solution: A poplar-based chlorine-doped carbon-supported ruthenium (Ru) hydrogen evolution electrocatalyst, using poplar biomass and waste polyvinyl chloride (PVC) as carbon and halogen sources, obtains a chlorine-doped porous carbon (Cl-C) support through co-pyrolysis and alkali activation, and loads metallic ruthenium nanoparticles on the surface of the support; the catalyst has a rich hierarchical pore structure, with mesopores accounting for more than 50%, and the pore size is concentrated in the range of 2-10 nm, exhibiting excellent hydrogen evolution catalytic activity and stability under acidic conditions.

[0009] The mass ratio of poplar wood to PVC is 1:0.2~1.

[0010] The loading of metallic ruthenium is 5 to 30% of the mass of the carbon support.

[0011] In a 0.5 M H2SO4 electrolyte, the overpotential corresponding to a current density of 10 mA / cm² is less than 150 mV, and the Tafel slope is less than 110 mV / dec.

[0012] A method for preparing the poplar-based chlorine-doped carbon-supported ruthenium hydrogen evolution electrocatalyst includes the following steps: S1. Mix poplar wood powder and waste PVC powder in a certain proportion and grind them evenly; S2. Pre-carbonize under a nitrogen atmosphere by heating to 400~500 ℃ and holding for 0.5~2 h; S3. Mix and grind the pre-carbonized product with alkali at a molar ratio of 1:0.4-1.2, and activate it at high temperature. Heat the temperature to 700-800 ℃ and keep it at that temperature for 1-2 h. After activation, cool it naturally to room temperature, wash it with acid, and then wash it with water and anhydrous ethanol alternately until it is neutral. Dry it under vacuum to obtain chlorine-doped poplar wood-based porous carbon support. S4. The carbon support is dispersed in a ruthenium salt solution, stirred for adsorption, dried, and then calcined and reduced under a nitrogen atmosphere to obtain the Ru@Cl–C catalyst.

[0013] The pre-carbonization heating rate is 2~5 ℃ / min; the activation heating rate is 2~5 ℃ / min.

[0014] The ruthenium salt is ruthenium trichloride hydrate, and the calcination reduction temperature is 500~700 ℃, and the time is 1~3 h.

[0015] The alkali mentioned is KOH or NaOH.

[0016] The chlorine doping can remove oxygen-containing groups on the surface of the carbon support in situ, improve the degree of carbon framework reduction, and enhance metal-support interaction, thereby improving the intrinsic activity and dispersibility of ruthenium active sites.

[0017] The application of the poplar-based chlorine-doped carbon-supported ruthenium electrocatalyst in hydrogen evolution by water electrolysis (HER) is characterized by its efficient and stable catalytic hydrogen evolution in a 0.5 M H2SO4 acidic system.

[0018] Beneficial effects This invention provides a poplar-based chlorine-doped carbon-supported ruthenium hydrogen evolution electrocatalyst. First, poplar and PVC are mixed and co-pyrolyzed to utilize the chlorine released during PVC pyrolysis, achieving in-situ chlorine doping of the carbon material and controlling its pore structure and electronic properties to obtain a chlorine-doped carbon precursor. Then, the chlorine-doped carbon precursor is activated with KOH to further optimize the specific surface area, pore distribution, and surface active sites of the carbon support. After washing and drying, a chlorine-doped activated carbon support is obtained. Finally, the ruthenium source precursor is mixed with the activated Cl-C support, and a hydrothermal calcination process is used to achieve uniform loading of the ruthenium active component. Subsequent post-processing yields the Ru@Cl-C catalyst. The catalyst is a black solid powder with extremely low density. The porosity of the porous structure of the support can be controlled by adjusting the mass ratio of poplar powder to waste PVC powder and the activation temperature. The carbon support has a rich hierarchical nanoporous structure and an ultra-high specific surface area. Furthermore, under the combined effects of chlorine doping, high-temperature calcination, and the confinement of the carbon support pores, ruthenium is stably anchored within the nanoporous structure of the carbon support, providing an ideal environment for efficient mass transfer and rapid hydrogen evolution reaction. This also avoids the activity reduction problem caused by ruthenium agglomeration during the catalytic reaction. This catalyst achieves highly efficient catalysis of the hydrogen evolution reaction and exhibits excellent stability in long-term electrochemical testing, demonstrating promising application prospects.

[0019] The poplar-based chlorine-doped carbon-supported ruthenium hydrogen evolution electrocatalyst of this invention has significant advantages over traditional hydrogen evolution catalysts, as detailed below: 1. Lower raw material costs and greater environmental value: Traditional hydrogen evolution catalysts mostly use fossil-based carbon as the carbon support, which is non-renewable, costly, and lacks environmental benefits in its preparation process. This invention uses abundant and widely available poplar biomass as the carbon source, combined with waste polyvinyl chloride (PVC) as the halogen source, achieving synergistic high-value utilization of agricultural and forestry waste and waste plastics. This reduces raw material costs and solves the environmental pollution problem caused by the accumulation of waste PVC, aligning with the concept of green and low-carbon development. The chlorine doping can remove oxygen-containing groups on the carbon support surface in situ, improve the reduction degree of the carbon skeleton, and enhance the metal-support interaction, thereby improving the intrinsic activity and dispersibility of ruthenium active sites.

[0020] 2. Superior Catalytic Activity: Traditional Ru-based catalysts generally suffer from Ru nanoparticle aggregation and insufficient exposure of active sites, and the metal-support interaction between the carbon support and Ru is weak, resulting in limited catalytic activity. This invention achieves in-situ chlorine doping through co-pyrolysis of poplar / PVC, and constructs a multi-level porous carbon support with high specific surface area and high defect density through high-temperature activation. Chlorine doping can effectively regulate the electronic structure of Ru active sites, strengthen the metal-support interaction, achieve high dispersion loading of Ru nanoparticles, and significantly improve the hydrogen evolution catalytic activity.

[0021] 3. Simpler preparation process and easier to scale up: The preparation of traditional high-performance hydrogen evolution catalysts often adopts complex template methods, microwave-assisted methods, etc., which are cumbersome and require high equipment, making it difficult to scale up production. This invention adopts a simple three-step process of "pyrolysis-activation-hydrothermal calcination", which is convenient to operate, requires conventional equipment, does not require complex reagents and harsh reaction conditions, has low preparation cost, is easy to realize large-scale industrial production, and has greater practical application value.

[0022] 4. Enhanced structural adjustability: Traditional carbon supports have limited adjustability in pore structure and surface properties, making it difficult to adapt to different hydrogen evolution reaction requirements. This invention can flexibly adjust the porosity, defect density, and Ru loading of the carbon support by controlling the mass ratio of poplar to PVC, activation temperature, hydrothermal and calcination parameters, thereby achieving precise control of catalyst performance and adapting to the hydrogen evolution requirements of water electrolysis in different scenarios, thus having a wider range of applications. Attached Figure Description

[0023] Figure 1 The images are scanning electron microscope (SEM) images of Examples 1 (unactivated poplar / PVC pre-carbonized product), Example 2 (Ru@C without halogen-doped Ru-based catalyst), and Example 3 (Ru@Cl–C with halogen catalyst) of the present invention. Among them, a is the SEM image of Example 1, b is the SEM image of Example 2, and c is the SEM image of Example 3.

[0024] Figure 2 This is the X-ray diffraction (XRD) pattern of Example 3 of the present invention (with halogen catalyst Ru@Cl–C).

[0025] Figure 3 The images show the Raman spectra of Examples 1 (unactivated poplar / PVC pre-carbonized product), Example 2 (undoped halogen Ru-based catalyst Ru@C), and Example 3 (with halogen catalyst Ru@Cl–C) of the present invention.

[0026] Figure 4 The image shows the X-ray photoelectron spectroscopy (XPS) spectrum of Example 3 of the present invention (with halogen catalyst Ru@Cl–C), where a is the full spectrum, b is the C 1s high-resolution spectrum, and c is the O 1s high-resolution spectrum.

[0027] Figure 5 The image shows the electrochemical test results for Example 3 of this invention (with halogenated catalyst Ru@Cl–C), where a is the LSV curve and b is the Tafel slope graph. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to specific embodiments. The specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0029] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available conventional products; the experimental methods used are all conventional methods and comply with the usual operating procedures of those skilled in the art, unless otherwise specified.

[0030] This invention provides a method for preparing a poplar-based chlorine-doped carbon-supported ruthenium hydrogen evolution electrocatalyst, comprising the following steps: S1. Preparation of poplar / PVC pre-carbonized products by pyrolysis: Weigh a certain amount of poplar powder and waste PVC powder, mix them evenly, and transfer them to a tube furnace for pyrolysis treatment; after pyrolysis, cool to room temperature, grind and crush the product, wash it alternately with deionized water and anhydrous ethanol, and dry it under vacuum to obtain poplar / PVC pre-carbonized products. S2. Activation preparation of chlorine-doped poplar-based porous carbon support: The poplar / PVC pre-carbonized product obtained in step A is mixed with NaOH in a certain proportion and ground evenly. The mixture is then transferred to a tube furnace for high-temperature activation treatment. After activation, the mixture is cooled to room temperature. The product is then washed with hydrochloric acid, followed by alternating washing with deionized water and anhydrous ethanol until neutral. After vacuum drying, the chlorine-doped poplar-based porous carbon support is obtained. S3. Preparation of catalyst by hydrothermal calcination of supported ruthenium: The chlorine-doped poplar-based porous carbon support obtained in step B was ultrasonically dispersed in deionized water to form a uniform suspension. Under stirring conditions, a ruthenium trichloride hydrate (RuCl3.xH2O) solution was slowly added to ensure full contact with the carbon support. After stirring until homogeneous, the solution was transferred to a hydrothermal reactor for hydrothermal reaction. After the hydrothermal reaction was completed, the solution was cooled to room temperature, the product was collected, washed, dried, and then transferred to a tube furnace for calcination and reduction under a nitrogen atmosphere. After calcination, the solution was cooled to room temperature to obtain the poplar-based chlorine-doped carbon-supported ruthenium hydrogen evolution electrocatalyst (Ru@Cl–C).

[0031] As a further improvement of the present invention, in step A, the mass ratio of poplar wood powder to waste PVC powder is 1:0.2-1; the pyrolysis treatment is carried out under a nitrogen atmosphere, with the temperature increased to 400-500℃ at a heating rate of 2-5℃ / min, and held for 0.5-2h.

[0032] As a further improvement of the present invention, in step B, the mass ratio of poplar / PVC pre-carbonized product to NaOH is 1:2-4; high-temperature activation is carried out under a nitrogen atmosphere, with the temperature increased to 700-800℃ at a heating rate of 2-5℃ / min, and the activation time is 1-2 hours.

[0033] As a further improvement of the present invention, in step C, the mass ratio of chlorine-doped poplar-based porous carbon support to ruthenium trichloride hydrate is 100:5-30; the hydrothermal reaction is maintained at 120-160°C for 8-12 hours.

[0034] As a further improvement of the present invention, in step C, the drying temperature after the hydrothermal reaction is 60-80℃, and the drying time is 4-6h.

[0035] As a further improvement of the present invention, in step C, the calcination reduction is heated to 500-700°C at a heating rate of 2-5°C / min and held for 1-3 hours; nitrogen gas is introduced for protection throughout the calcination reduction process, and the nitrogen flow rate is 50-100 mL / min.

[0036] Example 1: Preparation of unactivated poplar / PVC pre-carbonized products Weigh 1.0g of poplar powder and 0.5g of waste PVC powder, place them in a mortar and mix them evenly; transfer the mixture to a tube furnace, purge with nitrogen (nitrogen flow rate 80mL / min), heat to 450℃ at a heating rate of 5℃ / min, and maintain for 1h for pyrolysis treatment; after pyrolysis, allow to cool naturally to room temperature, grind and pulverize the product, wash with 200ml of hydrochloric acid (1mol / L), wash three times alternately with deionized water and anhydrous ethanol, and vacuum dry at 70℃ for 6h to obtain the unactivated poplar / PVC pre-carbonized product.

[0037] Example 2: Preparation of undoped halogen Ru-based catalyst (Ru@C) Step 1: Weigh 1.0g of poplar powder, grind it evenly in a mortar, and then transfer it to a tube furnace. Under nitrogen protection (nitrogen flow rate 80mL / min), heat it to 450℃ at 5℃ / min and pyrolyze it for 1h. After cooling, grind it into powder, wash it three times with deionized water and anhydrous ethanol alternately, and dry it under vacuum at 70℃ for 6h to obtain the pre-carbonized poplar product. Step 2: Mix and grind the above poplar pre-carbonized product with 2.5g NaOH until uniform, transfer to a tube furnace, heat to 750℃ at 5℃ / min under nitrogen protection, activate for 1.5h, cool and wash until neutral, and vacuum dry at 70℃ for 6h to obtain undoped halogen poplar-based porous carbon support. Step 3: Weigh 100 mg of the above undoped halogenated carbon support and ultrasonically disperse it in 20 mL of deionized water to form a uniform suspension; under stirring, slowly add 30 mg of ruthenium trichloride hydrate solution and continue stirring for 6 h; place the mixed solution in a 60 °C water bath to evaporate to dryness, and vacuum dry at 70 °C for 4 h; transfer the dried product to a tube furnace, under nitrogen protection (nitrogen flow rate 80 mL / min), heat to 600 °C at 5 °C / min, calcine and reduce for 2 h, and cool to room temperature to obtain the undoped halogenated Ru-based catalyst (Ru@C).

[0038] Example 3: Preparation of halogenated catalyst (Ru@Cl-C) Step 1: Weigh 1.0g of poplar powder and 0.5g of waste PVC powder, place them in a mortar and mix them evenly; transfer the mixture to a tube furnace, purge with nitrogen (nitrogen flow rate 80mL / min), heat to 450℃ at a heating rate of 5℃ / min, and maintain for 1h for pyrolysis treatment; after pyrolysis, allow to cool naturally to room temperature, grind and pulverize the product to prepare poplar / PVC pre-carbonized product (mass ratio of poplar powder to waste PVC powder 1:0.5). Step 2: Mix and grind the above poplar / PVC pre-carbonized product with 2.5g NaOH until uniform, transfer to a tube furnace, and heat to 750℃ at a heating rate of 5℃ / min under nitrogen protection (nitrogen flow rate 80mL / min) for 1.5h. After activation, allow to cool to room temperature naturally, wash with 200ml hydrochloric acid (1mol / L), and then wash alternately with deionized water and anhydrous ethanol until neutral. Dry under vacuum at 70℃ for 6h to obtain chlorine-doped poplar-based porous carbon support. Step 3: Weigh 100 mg of the above chlorine-doped carbon support and ultrasonically disperse it in 20 mL of deionized water to form a uniform suspension; under stirring, slowly add 30 mg of RuCl3·H2O solution and continue stirring for 6 h; place the mixed solution in a 60 °C water bath to evaporate to dryness, and vacuum dry at 70 °C for 4 h; transfer the dried product to a tube furnace, under nitrogen protection (nitrogen flow rate 80 mL / min), heat to 600 °C at 5 °C / min, calcine and reduce for 2 h, and cool to room temperature to obtain the halogenated catalyst (Ru@Cl–C).

[0039] Example 4: Preparation of halogenated catalysts (Ru@Cl-C) with different doping contents and reaction conditions Step 1: Weigh 1.0g of poplar wood powder and 1g of waste PVC powder, and mix them evenly in a mortar; transfer the mixture to a tube furnace, purge with nitrogen (nitrogen flow rate 80mL / min), and heat to 500℃ at a rate of 2℃ / min, maintaining the temperature for 0.5h for pyrolysis treatment; after pyrolysis, allow it to cool naturally to room temperature, grind and pulverize the product to prepare poplar wood / PVC pre-carbonized product (poplar wood powder to waste PVC powder mass ratio 1:1). Step 2: Mix and grind the above poplar / PVC pre-carbonized product with 3g NaOH until uniform, transfer to a tube furnace, and heat to 800℃ at a heating rate of 2℃ / min under nitrogen protection (nitrogen flow rate 80mL / min) for 1h activation. After activation, cool naturally to room temperature, wash with 200ml hydrochloric acid (1mol / L), and then wash alternately with deionized water and anhydrous ethanol until neutral. Dry under vacuum at 70℃ for 6h to obtain chlorine-doped poplar-based porous carbon support. Step 3: Weigh 100 mg of the above chlorine-doped carbon support and ultrasonically disperse it in 20 mL of deionized water to form a uniform suspension; under stirring conditions, slowly add 30 mg of RuCl3·H2O solution and continue stirring for 6 h; place the mixed solution in a 60 °C water bath to evaporate to dryness, and vacuum dry at 70 °C for 4 h; transfer the dried product to a tube furnace, under nitrogen protection (nitrogen flow rate 80 mL / min), heat to 600 °C at 2 °C / min, calcine and reduce for 2 h, and cool to room temperature to obtain the halogenated catalyst (Ru@Cl–C).

[0040] Example 5: Preparation of halogenated catalysts (Ru@Cl-C) with different doping contents and reaction conditions Step 1: Weigh 1.0g of poplar powder and 2g of waste PVC powder, and mix them evenly in a mortar; transfer the mixture to a tube furnace, purge with nitrogen (nitrogen flow rate 80mL / min), and heat to 400℃ at a rate of 3℃ / min, maintaining the temperature for 2h for pyrolysis; after pyrolysis, allow it to cool naturally to room temperature, grind and pulverize the product to prepare poplar / PVC pre-carbonized product (poplar powder to waste PVC powder mass ratio 1:2). Step 2: Mix and grind the above poplar / PVC pre-carbonized product with 5g NaOH until uniform, transfer to a tube furnace, and heat to 700℃ at a heating rate of 3℃ / min under nitrogen protection (nitrogen flow rate 80mL / min) for 2h activation. After activation, cool naturally to room temperature, wash with 200ml hydrochloric acid (1mol / L), and then wash alternately with deionized water and anhydrous ethanol until neutral. Vacuum dry at 70℃ for 6h to obtain chlorine-doped poplar-based porous carbon support. Step 3: Weigh 100 mg of the above chlorine-doped carbon support and ultrasonically disperse it in 20 mL of deionized water to form a uniform suspension; under stirring conditions, slowly add 30 mg of RuCl3·H2O solution and continue stirring for 6 h; place the mixed solution in a 60 °C water bath to evaporate to dryness, and vacuum dry at 70 °C for 4 h; transfer the dried product to a tube furnace, under nitrogen protection (nitrogen flow rate 80 mL / min), heat to 600 °C at 3 °C / min, calcine and reduce for 2 h, and cool to room temperature to obtain the halogenated catalyst (Ru@Cl–C).

Claims

1. A poplar-based chlorine-doped carbon supported ruthenium (Ru) electrocatalyst for hydrogen evolution, characterized in that: Using poplar biomass and waste polyvinyl chloride (PVC) as carbon and halogen sources, a chlorine-doped porous carbon (Cl-C) support was obtained through co-pyrolysis and alkali activation, and metallic ruthenium nanoparticles were loaded on the surface of the support. The catalyst has a rich hierarchical pore structure, with mesopores accounting for more than 50% and pore sizes concentrated in the range of 2-10 nm. It exhibits excellent hydrogen evolution catalytic activity and stability under acidic conditions.

2. The electrocatalyst according to claim 1, characterized in that: The mass ratio of poplar wood to PVC is 1:0.2~1.

3. The electrocatalyst according to claim 1, characterized in that: The loading of metallic ruthenium is 5 to 30% of the mass of the carbon support.

4. The electrocatalyst according to claim 1, characterized in that: In a 0.5 M H2SO4 electrolyte, the overpotential corresponding to a current density of 10 mA / cm² is less than 150 mV, and the Tafel slope is less than 110 mV / dec.

5. A method for preparing the poplar-based chlorine-doped carbon-supported ruthenium hydrogen evolution electrocatalyst according to any one of claims 1 to 4, characterized in that, Includes the following steps: S1. Mix poplar wood powder and waste PVC powder in a certain proportion and grind them evenly; S2. Pre-carbonize under a nitrogen atmosphere by heating to 400~500 ℃ and holding for 0.5~2 h; S3. Mix and grind the pre-carbonized product with alkali at a molar ratio of 1:0.4-1.2, and activate it at high temperature. Heat the temperature to 700-800 ℃ and keep it at that temperature for 1-2 h. After activation, cool it naturally to room temperature, wash it with acid, and then wash it with water and anhydrous ethanol alternately until it is neutral. Dry it under vacuum to obtain chlorine-doped poplar wood-based porous carbon support. S4. The carbon support is dispersed in a ruthenium salt solution, stirred for adsorption, dried, and then calcined and reduced under a nitrogen atmosphere to obtain the Ru@Cl–C catalyst.

6. The preparation method according to claim 5, characterized in that: The pre-carbonization heating rate is 2~5 ℃ / min; the activation heating rate is 2~5 ℃ / min.

7. The preparation method according to claim 5, characterized in that: The ruthenium salt is ruthenium trichloride hydrate, and the calcination reduction temperature is 500~700 ℃, and the time is 1~3 h.

8. The preparation method according to claim 5, characterized in that: The alkali mentioned is KOH or NaOH.

9. The application of the poplar-based chlorine-doped carbon-supported ruthenium electrocatalyst according to any one of claims 1 to 4 in hydrogen evolution electrolysis (HER), characterized in that: It can efficiently and stably catalyze hydrogen evolution in an acidic system of 0.5 M H2SO4.

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