A vacancy-rich Ru / RuSe x Heterogeneous electrocatalysts, their preparation methods and applications

Abstract

This invention belongs to the fields of new energy nanomaterials technology and water electrolysis for hydrogen production, specifically relating to a vacancy-rich Ru / RuSe. x Heterogeneous electrocatalysts, their preparation methods, and applications. The electrocatalyst consists of a cubic RuSe2 matrix rich in selenium vacancies and uniformly distributed and stably anchored metallic Ru nanoparticles on the RuSe2 surface. The preparation method includes the following steps: hydrothermal synthesis of the precursor RuSe2 powder, followed by Joule heating of the RuSe2 powder under an inert or reducing atmosphere to obtain vacancy-rich Ru / RuSe2. x Heterogeneous electrocatalyst. The catalyst of this invention exhibits excellent hydrogen evolution performance under alkaline water and alkaline seawater conditions, achieving 10 mA·cm⁻¹ hydrogen evolution per minute (T1). ‑2 Overpotentials of only 21 mV and 26 mV at current densities; and capable of operating at 800 mA·cm⁻¹. ‑2 Stable operation for 400 hours at current density.

Description

Technical Field

[0001] This invention belongs to the fields of new energy nanomaterials technology and water electrolysis for hydrogen production, specifically relating to a vacancy-rich Ru / RuSe. x Heterogeneous electrocatalysts, their preparation methods, and applications. Background Technology

[0002] With the rapid development of clean energy technologies, hydrogen production through water electrolysis has become an important pathway for the large-scale application of hydrogen energy due to its advantages of zero carbon emissions, high purity, and renewable energy. The key to improving electrolysis efficiency lies in developing high-performance electrocatalysts. Platinum (Pt), a precious metal, has long been considered an ideal catalyst for the hydrogen evolution reaction (HER) due to its near-thermodynamically optimal hydrogen adsorption free energy. However, the scarcity and high price of platinum resources severely limit its large-scale industrial application. Ruthenium (Ru), as a relatively abundant non-platinum precious metal with excellent electrocatalytic performance, has attracted widespread attention. However, the negative hydrogen adsorption free energy of Ru leads to excessive adsorption of hydrogen intermediates, hindering hydrogen release and limiting its HER catalytic performance, especially in complex electrolysis environments such as alkaline environments or seawater.

[0003] To overcome the drawbacks of hydrogen adsorption in Ru, researchers have proposed constructing Ru-based compounds. Among them, ruthenium selenide (RuSe2) has attracted widespread attention in hydrogen evolution electrocatalysis due to its stable crystal structure, moderate band gap, and tunable electronic structure. The introduction of Se can regulate the electronic state distribution of Ru's d orbitals, improving its hydrogen adsorption behavior and enhancing reaction activity. However, RuSe2 itself has poor electrical conductivity, limited electron transport, and limited exposure of its catalytic active sites, making it difficult to achieve efficient HER catalysis alone. To further improve catalytic performance, it is urgent to enhance performance through structural design, such as constructing heterointerfaces and controlling defect structures.

[0004] Existing methods for synthesizing ruthenium-based catalysts and their heterostructures mostly rely on traditional heat treatment processes such as high-temperature calcination, hydrothermal reaction, and atmospheric reduction. These methods typically suffer from high energy consumption, long reaction times, and imprecise structural control, making it difficult to achieve precise control over interface morphology and vacancy defects, thus affecting the stability of catalytic performance and industrial scale-up applications.

[0005] In recent years, Joule heating technology has emerged as a rapid material synthesis method, attracting attention in the field of electrocatalytic material preparation due to its advantages such as fast heating rate, low energy consumption, and strong local thermal effect. This technology achieves rapid heating by directly applying current to conductive precursors, while simultaneously creating a local reducing environment within the material. This environment facilitates the reduction of metal ions and the formation of vacancy defects, providing a new synthetic route for constructing Ru-based catalytic materials with optimized structure and controllable defects. Summary of the Invention

[0006] The purpose of this invention is to solve the problems of low activity, poor stability and complex preparation process that are difficult to precisely control in existing alkaline water / alkaline seawater Ru-based hydrogen evolution catalysts, and to provide a vacancy-rich heterostructure electrocatalyst with simple preparation method, high catalytic activity, strong stability and suitable for long-term operation at high current density.

[0007] Specifically, the present invention provides a vacancy-rich Ru / RuSe. x A heterostructured electrocatalyst is proposed, comprising a cubic RuSe2 matrix rich in selenium vacancies and uniformly distributed and stably anchored metallic Ru nanoparticles on the RuSe2 surface; the cubic RuSe2 matrix rich in selenium vacancies belongs to the Pa3 group. - The space group is a cubic crystal system, in which Ru atoms are located at face-centered cubic lattice positions, and Se atoms form Se2 pairs and fill the octahedral interstitial sites in the crystal system to form a stable Ru-Se coordination structure; the selenium vacancies exhibit a uniform distribution in the matrix and are preferentially enriched along high-energy crystal planes; the metallic Ru nanoparticles anchored on the RuSe2 surface have a clear heterogeneous interface with the matrix and are tightly anchored through bonding.

[0008] The heterostructure effectively optimizes the electronic structure and hydrogen adsorption energy by regulating the interface between selenium vacancies and metal Ru, significantly improving the catalytic activity and long-term stability of the hydrogen evolution reaction.

[0009] The catalyst has an average size of 30-80 nm, and the Ru nanoparticles have an average size of 2-8 nm.

[0010] This invention also provides a vacancy-rich Ru / RuSe. x A method for preparing heterostructured electrocatalysts, comprising the following steps:

[0011] The precursor RuSe2 powder is synthesized via a hydrothermal method, and then subjected to Joule heating treatment in an inert or reducing atmosphere to obtain vacancy-rich Ru / RuSe. x Heterogeneous electrocatalysts.

[0012] Specifically, the hydrothermal synthesis of the precursor RuSe2 powder includes the following steps:

[0013] (1) Disperse RuCl3·3H2O in deionized water, add disodium ethylenediaminetetraacetate and stir for 0.5~2 hours to prepare complex solution A;

[0014] (2) Dissolve Se powder in concentrated KOH aqueous solution to prepare solution B;

[0015] (3) Slowly add complex solution A to solution B and mix evenly. Transfer to a high-pressure reactor and hydrothermally react at 140~200℃ for 8~36 hours. After cooling, centrifuge until pH is neutral and dry to obtain RuSe2 powder.

[0016] Preferably, the inert atmosphere is one of argon, nitrogen, and helium, and the reducing atmosphere is one of hydrogen-containing argon, hydrogen-containing nitrogen, and hydrogen-containing helium.

[0017] Preferably, the Joule heating is performed using a constant current of 25-60 A, with a heating temperature of 380-600°C, and held for 15-120 seconds.

[0018] Preferably, the Joule heating is performed using a constant current of 43~48 A, and the heating temperature is preferably 550~600℃.

[0019] Preferably, the molar ratio of RuCl3·3H2O, disodium ethylenediaminetetraacetate, and Se is 1:(1.2~2):(1.5~3).

[0020] Preferably, the concentration of RuCl3·3H2O is 0.05~0.3 g / mL, and the concentration of KOH is 15~20 M.

[0021] This invention also provides a vacancy-rich Ru / RuSe. x The application of heterostructured electrocatalysts involves using the catalyst in the electrolysis of seawater to produce hydrogen.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The heterostructured electrocatalyst Ru / RuSe of the present invention x The Ru nanoparticles possess near-zero hydrogen adsorption free energy and have Se vacancies that modulate the d-band centers of RuSe2, enhancing water dissociation activity. The heterostructure facilitates electron transport, achieving a dissociation rate of 10 mA·cm⁻¹. -2 The overpotential is only 21 mV in alkaline water and 26 mV in alkaline seawater at the current density, which is superior to most reported Ru-based catalysts and commercial 20% Pt / C catalysts.

[0024] 2. The catalyst prepared by this invention can achieve a flux of 800 mA·cm⁻¹ in a self-assembled electrolyzer. -2 It operated stably for over 400 hours at a current density without any change in cell voltage, demonstrating excellent prospects for industrial applications and is expected to be used for large-scale electrolysis of seawater to produce hydrogen.

[0025] 3. The preparation method of this invention uses Joule heating to improve the crystallinity of the material, while inducing in-situ reduction of Ru and generation of Se vacancies. This not only avoids the problems of long heating time, high energy consumption, complex process and nanoparticle agglomeration of traditional high-temperature reducing atmosphere calcination, but also allows for rapid control of defect concentration.

[0026] 4. The preparation method of this invention not only achieves in-situ reduction and loading of metallic Ru nanoparticles, but also induces the generation of Se vacancies, effectively improving the conductivity, active site density and interface stability of the material, regulating the electronic structure of the material, enhancing water dissociation, optimizing hydrogen adsorption free energy, and exhibiting excellent performance and long-term stability in the hydrogen evolution reaction of alkaline water and seawater. Attached Figure Description

[0027] Figure 1 (a) Ru / RuSe prepared in Example 1 x -43 Scanning electron microscope (SEM) image of the catalyst, (b) is the calculated average particle size of the catalyst.

[0028] Figure 2 (a) Ru / RuSe prepared in Example 1 x (a) Transmission electron microscopy (TEM) image of the -43 catalyst, and (b) is the average particle size calculation diagram of the Ru nanoparticles.

[0029] Figure 3 Ru / RuSe prepared in Example 1 x Electron paramagnetic resonance (EPR) diagrams of RuSe2 prepared by catalyst -43 and Comparative Example 1.

[0030] Figure 4 Ru / RuSe prepared in Examples 1-4 x -33.Ru / RuSe x -38、Ru / RuSe x -43.Ru / RuSe x X-ray diffraction patterns of the catalyst and the RuSe2 and RuSe2-T catalysts prepared in Comparative Examples 1 and 2, (a) is a comparison diagram of Examples 1-4 and Comparative Example 1, and (b) is a comparison diagram of Example 1 and Comparative Example 2.

[0031] Figure 5 Ru / RuSe prepared in Example 1 x High-resolution transmission electron microscopy image of the -43 catalyst.

[0032] Figure 6Polarization curves of the catalysts prepared in Example 1 and Comparative Examples 1 and 2, and the commercial catalyst 20% Pt / C, were obtained by linear sweep voltammetry (LSV) in alkaline water and alkaline seawater. Figure (a) shows the polarization curves of 1M KOH aqueous solution and Figure (b) shows the polarization curves of 1M KOH + real seawater.

[0033] Figure 7 The overpotential data obtained by LSV testing of the catalysts prepared in Examples 1-4 and Comparative Example 1, and the commercial catalyst 20% Pt / C in alkaline water and alkaline seawater at different current densities are shown in Figure (a) for 1M KOH aqueous solution and Figure (b) for 1M KOH + real seawater.

[0034] Figure 8 The electrochemical impedance spectroscopy (EIS) spectra of the catalysts prepared in Example 1 and Comparative Examples 1 and 2, and the commercial catalyst 20% Pt / C under open-circuit potential conditions in alkaline water and alkaline seawater are shown in Figure (a) and Figure (b) respectively. The catalysts prepared in Example 1 and Comparative Examples 1 and 2, and the commercial catalyst 20% Pt / C are shown in Figure (b) respectively.

[0035] Figure 9 The catalyst prepared in Example 1 was assembled into an anion exchange membrane flow electrolyzer and tested in alkaline seawater at 800 mA·cm⁻¹. -2 Long-term stability test curves at current density. Detailed Implementation

[0036] The following examples further illustrate specific implementations of the present invention, but the implementation and protection of the present invention are not limited thereto. It should be noted that any processes not specifically described below are those that can be implemented or understood by those skilled in the art by referring to existing technology. Reagents or instruments whose manufacturers are not specified are considered to be conventional products that can be purchased commercially.

[0037] Example 1

[0038] Heterogeneous electrocatalyst Ru / RuSe x Preparation:

[0039] (1) Preparation of precursor RuSe2 powder

[0040] ① Disperse 2.62 mL of RuCl3·3H2O with a concentration of 50 mg / mL in 20 mL of deionized water, add 0.8 mmol of disodium ethylenediaminetetraacetate and stir for 1 hour to prepare complex solution A;

[0041] ② Dissolve 1 mmol of Se powder in 5 mL of 20 M KOH aqueous solution to prepare solution B;

[0042] ③ Slowly add complex solution A to solution B and mix thoroughly. Transfer the mixture to a high-pressure reactor and place it in a 180°C oven for hydrothermal reaction for 24 hours. After naturally cooling to room temperature, centrifuge the mixture and wash it until the pH of the supernatant is neutral. Then dry it to obtain RuSe2 powder.

[0043] (2) Joule heating treatment

[0044] ① The RuSe2 powder is evenly dispersed on conductive carbon paper, and the two ends of the carbon paper are fixed to the electrodes of the Joule heating device. Argon atmosphere is then introduced into the device.

[0045] ② A constant current of 43 A is applied, and the mixture is heated to 550°C and held at that temperature for 40 seconds to form a heterostructure electrocatalyst containing metallic Ru nanoparticles and selenium vacancies, labeled as Ru / RuSe. x -43.

[0046] Example 2

[0047] Step (2) ② The constant current is 33 A, and the temperature is heated to 380°C. The remaining steps are the same as in Example 1, labeled as Ru / RuSe. x -33.

[0048] Example 3

[0049] Step (2) ② A constant current of 38 A is applied, and the temperature is heated to 470°C. The remaining steps are the same as in Example 1, labeled as Ru / RuSe. x -38.

[0050] Example 4

[0051] Step (2) ② A constant current of 48 A is used to heat to 600°C. The remaining steps are the same as in Example 1, labeled Ru / RuSe. x -48.

[0052] Example 5

[0053] Heterogeneous electrocatalyst Ru / RuSe x Preparation:

[0054] (1) Preparation of precursor RuSe2 powder

[0055] ① Disperse 1.31 mL of RuCl3·3H2O with a concentration of 100 mg / mL in 20 mL of deionized water, add 1.0 mmol of disodium ethylenediaminetetraacetate and stir for 0.5 hours to prepare complex solution A;

[0056] ② Dissolve 1.5 mmol of Se powder in 7.5 mL of 18 M concentrated KOH aqueous solution to prepare solution B;

[0057] ③ Slowly add complex solution A to solution B and mix well. Transfer to a high-pressure reactor and place in a 140℃ oven for hydrothermal reaction for 36 hours. After naturally cooling to room temperature, centrifuge the mixture and wash until the pH is neutral. Then dry to obtain RuSe2 powder.

[0058] (2) Joule heating treatment

[0059] ① The RuSe2 powder is evenly dispersed on conductive carbon paper, and the two ends of the carbon paper are fixed to the electrodes of the Joule heating device. Then, an argon atmosphere containing hydrogen is introduced into the device.

[0060] ② A constant current of 60 A is applied, and the temperature is heated to 550℃. The temperature is then maintained for 15 seconds to form a heterostructure electrocatalyst containing metallic Ru nanoparticles and selenium vacancies.

[0061] Example 6

[0062] Heterogeneous electrocatalyst Ru / RuSe x Preparation:

[0063] (1) Preparation of precursor RuSe2 powder

[0064] ① Disperse 0.66 mL of RuCl3·3H2O with a concentration of 200 mg / mL in 20 mL of deionized water, add 0.6 mmol of disodium ethylenediaminetetraacetate and stir for 2 hours to prepare complex solution A;

[0065] ② Dissolve 0.75 mmol of Se powder in 3.75 mL of 15 M concentrated KOH aqueous solution to prepare solution B;

[0066] ③ Slowly add complex solution A to solution B and mix well. Transfer to a high-pressure reactor and place in a 200℃ oven for hydrothermal reaction for 8 hours. After naturally cooling to room temperature, centrifuge the mixture and wash until the pH is neutral. Finally, dry to obtain RuSe2 powder.

[0067] (2) Joule heating treatment

[0068] ① The RuSe2 powder is evenly dispersed on conductive carbon paper, and the two ends of the carbon paper are fixed to the electrodes of the Joule heating device. Nitrogen atmosphere is then introduced into the device.

[0069] ② A constant current of 25A is applied, and the temperature is heated to 380℃. The temperature is then maintained for 120 seconds to form a heterostructure electrocatalyst containing metallic Ru nanoparticles and selenium vacancies.

[0070] Comparative Example 1

[0071] The RuSe2 powder obtained in step one was not subjected to Joule heating treatment, and the remaining steps were the same as in Example 1, and it was labeled as RuSe2.

[0072] Comparative Example 2

[0073] Step (1) is the same as in Example (1);

[0074] (2) Preparation of RuSe2-T powder:

[0075] ① Weigh 100 mg of the RuSe2 powder obtained in step one, place it in an alumina ceramic boat, transfer it to a tube furnace, and maintain a temperature of 50 mL / min. -1 Argon gas introduction rate: 30 minutes;

[0076] ② Heat treatment is performed under an argon atmosphere. The specific heating rate is set to 5 °C / min. -1 The temperature was raised from room temperature to 550 °C, held for 2 hours, and then naturally cooled to room temperature to obtain the heat-treated RuSe2 sample, which was labeled as RuSe2-T.

[0077] Experimental Example 1: Catalyst Characterization Tests

[0078] 1. The Ru / RuSe obtained in Example 1 x The -43 catalyst was tested using scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

[0079] (1) By Figure 1 It can be seen that Ru / RuSe was prepared in Example 1. x SEM images of the -43 catalyst show a well-dispersed near-spherical nanoparticle structure with an average size of 52.8 nm.

[0080] (2) By Figure 2 It can be seen that Ru / RuSe was prepared in Example 1. x TEM images of the -43 catalyst show that ultra-small Ru metal nanoparticles are uniformly distributed and stably anchored on the RuSe2 surface. Image processing and statistical analysis indicate that the average particle size of the Ru nanoparticles is approximately 4.0 nm.

[0081] 2. The Ru / RuSe obtained in Example 1 x Electron paramagnetic resonance (EPR) tests were performed on the catalyst and RuSe2 prepared in Comparative Example 1.

[0082] Depend on Figure 3 It can be seen that Ru / RuSe was prepared in Example 1.x The EPR spectrum of the -43 catalyst showed a strong selenium vacancy signal at g=2.003, which contrasted sharply with the comparative example 1, which had no vacancy signal.

[0083] 3. The Ru / RuSe obtained in Examples 1-4 x -33.Ru / RuSe x -38、Ru / RuSe x -43.Ru / RuSe x X-ray diffraction (XRD) was performed on the -48 catalyst and the RuSe2 and RuSe2-T catalysts prepared in Comparative Examples 1 and 2.

[0084] Depend on Figure 4 (a) It can be seen that the XRD pattern of RuSe2 prepared in Comparative Example 1 shows that it has low crystallinity and two weak and broad characteristic peaks at 30° and 55°, which is consistent with the hexagonal phase structure of transition metal dichalcogenides; Ru / RuSe2 prepared in Examples 1-4 x -33.Ru / RuSe x -38、Ru / RuSe x -43.Ru / RuSe x The XRD pattern of the -48 catalyst shows that it has characteristic diffraction peaks similar to those of cubic RuSe2 and high crystallinity, while also exhibiting characteristic peaks of the (101) crystal plane of hexagonal metallic Ru. Figure 4 (b) It can be seen that Comparative Example 2 only has the characteristic diffraction peaks of cubic phase RuSe2.

[0085] 4. The Ru / RuSe obtained in Example 1 x The catalyst was tested using high-resolution transmission electron microscopy (HRTEM).

[0086] Figure 5 The HRTEM images show that the lattice fringe spacing of the nanoparticles is 0.234 nm and 0.205 nm, which correspond to the (100) and (101) crystal planes of hexagonal close-packed ruthenium metal, respectively; in addition, the lattice fringe spacing of the (311) crystal plane of cubic phase RuSe2, with a spacing of 0.178 nm, was also observed.

[0087] Experiment Example 2: Electrochemical Performance Testing

[0088] 1. Electrode material fabrication

[0089] The catalysts prepared in Example 1 and Comparative Examples 1 and 2, as well as the commercial catalyst 20% Pt / C, were dispersed in a mixed solvent containing 950 μL ethanol and 50 μL perfluorosulfonic acid resin, followed by ultrasonic treatment for 30 minutes to obtain a slurry. The resulting slurry was sprayed onto a carbon paper substrate on a heated plate using an air spray gun, with a catalyst loading of 1.0 mg·cm³. -2 .

[0090] 2. Testing Methods

[0091] Electrochemical performance was tested in a three-electrode system, with an Hg / HgO electrode as the reference electrode, a graphite rod electrode as the counter electrode, and carbon paper coated with catalyst as the working electrode. A 1 M KOH aqueous solution or seawater solution was used as the electrolyte. The potential reference was a reversible hydrogen electrode (RHE). E RHE = E Hg / HgO +0.098 + 0.0592 × pH. Calculate the overpotential (η) according to the following equation: η = E RHE Polarization profiles were obtained by linear sweep voltammetry (LSV) at a scan rate of 5 mV / s, and all LSV-obtained polarization profiles were compensated for 95% resistance-voltage drop. Electron transport properties were obtained by AC impedance testing in alkaline water and alkaline seawater solutions at open-circuit potential.

[0092] 3. Test Results

[0093] Depend on Figure 6 As can be seen from the linear sweep voltammetry (LSV) plots (a) and (b), compared to the catalysts prepared in Comparative Examples 1 and 2 of this invention and the commercial catalyst 20% Pt / C, the Ru / RuSe prepared in Example 1... x The -43 catalyst exhibits superior performance in both alkaline water and alkaline seawater. The RuSe2 catalyst prepared in Comparative Example 1 has the lowest polarization current; after Joule heating treatment, the polarization current density significantly increases, resulting in a marked improvement in hydrogen evolution activity. Furthermore, compared to the RuSe2-T catalyst treated in a tube furnace, the Ru / RuSe catalyst of this invention... x The -43 catalyst exhibits better hydrogen evolution catalytic activity.

[0094] Depend on Figure 7 (a) It can be seen that Ru / RuSe x -43 catalyst at 10 mA·cm -2 100 mA·cm -2 and 200 mA·cm -2At current densities, the overpotentials were as low as 21 mV, 78 mV and 115 mV, respectively, which were significantly lower than those of RuSe2 prepared in Comparative Example 1 (55 mV, 165 mV, 224 mV) and commercial 20% Pt / C catalyst (25 mV, 129 mV, 190 mV).

[0095] Depend on Figure 7 As shown in (b), Ru / RuSe x -43 catalyst at 10 mA·cm -2 100 mA·cm -2 and 200 mA·cm -2 The overpotentials at current densities were 26 mV, 101 mV, and 150 mV, respectively, which were significantly lower than those of the RuSe2 prepared in Comparative Example 1 and the commercial 20% Pt / C catalyst.

[0096] Depend on Figure 8 It can be seen that the Ru / RuSe prepared in Example 1 x The -43 catalyst exhibits lower AC impedance under open-circuit potential conditions in alkaline water and alkaline seawater compared to the catalysts prepared in Comparative Examples 1 and 2, and the commercial catalyst 20%Pt / C.

[0097] Table 1 compares the hydrogen evolution activities of other ruthenium-based or selenium-based electrocatalysts with those of the catalyst of this invention in 1M KOH and alkaline seawater. (Ru / RuSe of this invention) x The overpotentials at -43 were 21 mV and 26 mV, respectively, which are lower than those of other catalysts. This demonstrates the effectiveness of the Ru / RuSe catalyst of this invention. x Its hydrogen evolution activity is superior to that of other previously reported ruthenium-based or selenium-based electrocatalysts.

[0098] Table 1 Comparison of hydrogen evolution activity of other ruthenium-based or selenium-based electrocatalysts and the catalyst of this invention in 1M KOH and alkaline seawater.

[0099]

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[0108] Experimental Example 3: Anion Exchange Membrane Electrolyzer Test

[0109] 1. Testing Methods

[0110] The catalyst was further assembled into a membrane electrode, with Example 1 as the cathode and a self-made foamed nickel-supported layered nickel-iron bimetallic hydroxide as the anode, assembled on both sides of the anion exchange membrane to form a complete electrolyzer, and an anion exchange membrane water electrolyzer test was conducted.

[0111] 2. Test Results

[0112] Depend on Figure 9 It can be seen that the system exhibits excellent long-term stability in alkaline seawater environment, with a current density reaching 800 mA·cm⁻¹. -2 At that time, the required applied voltage was 2.08 V, and after 400 hours of continuous constant current operation, the electrolyzer voltage showed almost no increase; a stable hydrogen evolution reaction was achieved under industrial-grade current density in alkaline seawater conditions.

[0113] The above embodiments are merely preferred embodiments of the present invention and are only used to explain the present invention, not to limit the present invention. Any changes, substitutions, modifications, etc., made by those skilled in the art without departing from the spirit and essence of the present invention should be within the protection scope of the present invention.

Claims

1. A vacancy-rich Ru / RuSe x Heterogeneous electrocatalyst, characterized in that, The electrocatalyst consists of a cubic RuSe2 matrix rich in selenium vacancies and uniformly distributed and stably anchored metallic Ru nanoparticles on the RuSe2 surface; the cubic RuSe2 matrix rich in selenium vacancies belongs to Pa. 3- The space group is a cubic crystal system, in which Ru atoms are located at face-centered cubic lattice positions, and Se atoms form Se2 pairs and fill the octahedral interstitial sites in the crystal system to form a stable Ru-Se coordination structure; the selenium vacancies exhibit a three-dimensional uniform distribution in the matrix and are preferentially enriched along high-energy crystal planes; the metallic Ru nanoparticles anchored on the RuSe2 surface have a clear heterogeneous interface with the matrix and are tightly anchored through bonding.

2. The vacancy-rich Ru / RuSe according to claim 1 x Heterogeneous electrocatalyst, characterized in that, The electrocatalyst has an average size of 30-80 nm, and the Ru nanoparticles have an average size of 2-8 nm.

3. A vacancy-rich Ru / RuSe as described in claim 1 or 2 x A method for preparing heterostructured electrocatalysts, characterized in that, The method includes the following steps: The precursor RuSe2 powder is synthesized via a hydrothermal method, and then subjected to Joule heating treatment in an inert or reducing atmosphere to obtain vacancy-rich Ru / RuSe. x Heterogeneous electrocatalysts.

4. The preparation method according to claim 3, characterized in that, The hydrothermal synthesis of the precursor RuSe2 powder specifically includes the following steps: (1) Disperse RuCl3·3H2O in deionized water, add disodium ethylenediaminetetraacetate and stir for 0.5~2 hours to prepare complex solution A; (2) Dissolve Se powder in concentrated KOH aqueous solution to prepare solution B; (3) Slowly add complex solution A to solution B and mix evenly. Transfer to a high-pressure reactor and hydrothermally react at 140~200℃ for 8~36 hours. After cooling, centrifuge until pH is neutral and dry to obtain RuSe2 powder.

5. The preparation method according to claim 3, characterized in that, The inert atmosphere is one of argon, nitrogen, and helium, and the reducing atmosphere is one of hydrogen-containing argon, hydrogen-containing nitrogen, and hydrogen-containing helium.

6. The preparation method according to claim 3, characterized in that, The Joule heating is performed using a constant current of 25~60 A, with a heating temperature of 380~600℃, and held for 15~120 seconds.

7. The preparation method according to claim 6, characterized in that, The Joule heating is performed using a constant current of 43A~48A, and the heating temperature is 550~600℃.

8. The preparation method according to claim 4, characterized in that, The molar ratio of RuCl3·3H2O, disodium ethylenediaminetetraacetate, and Se is 1:(1.2~2):(1.5~3).

9. The preparation method according to claim 4, characterized in that, The concentration of RuCl3·3H2O is 0.05~0.3 g / mL, and the concentration of concentrated KOH is 15~20 M.

10. A vacancy-rich Ru / RuSe as described in claim 1 or 2 x The application of heterostructured electrocatalysts is characterized by, The electrocatalyst is used to produce hydrogen through the electrolysis of seawater.

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