An electrocatalyst for hydrogen production by seawater electrolysis, its preparation method and application

Abstract

The present invention relates to the technical field of catalysts, and particularly relates to an electrocatalyst for hydrogen production by seawater electrolysis, a preparation method thereof, and an application thereof. The electrocatalyst uses titanium carbide nanofibers as a carrier and is loaded with ruthenium nanoparticles. The present invention obtains titanium carbide nanofibers by electrospinning. The nanofibers not only have a large specific surface area, which is conducive to the loading of ruthenium nanoparticles; there is a metal-support interaction between ruthenium and the carbide, which can stably load ruthenium nanoparticles and solve the problem that ruthenium nanoparticles are prone to agglomeration; therefore, the formed electrocatalyst Ru@TiC has a larger specific surface area and richer chemical reaction active sites, making the catalyst have higher catalytic reaction activity. In addition, due to the good chemical stability and corrosion resistance of Ru@TiC, it can not only carry out efficient electrolytic water hydrogen production in a pure water environment under acidic or alkaline conditions, but also carry out efficient electrolytic seawater hydrogen production under acidic or alkaline conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly relates to an electrocatalyst for seawater electrolysis to produce hydrogen, a preparation method thereof, and an application thereof. Background Art

[0002] Disclosing the information of this background art section is only intended to enhance the overall understanding of the present invention, and it is not necessarily regarded as an admission or an implication in any form that this information constitutes the prior art already known to those of ordinary skill in the art.

[0003] As one of the important chemical raw materials and emerging energy sources, hydrogen is widely used in fields such as chemical production, electronics industry, aerospace, etc. The electrolysis of water to produce hydrogen is a clean method for large-scale production of high-purity hydrogen. However, electrolysis of water to produce hydrogen requires a large amount of high-purity water, but the fresh water resources on the earth are becoming increasingly scarce. As the most abundant water resource on the earth, realizing direct electrolysis of seawater to produce hydrogen has important significance.

[0004] Currently, one of the most promising catalysts for seawater electrolysis to produce hydrogen for commercial use is Pt nanoparticles supported on carbon black or activated carbon (Pt / C). By using carbon black or activated carbon as a carrier, mixing it with chloroplatinic acid solution, and then through steps such as drying, reduction, heat treatment, washing, etc., Pt nanoparticles with a particle size of about 3 - 5 nm are obtained and distributed on the surface of the carbon carrier. Although this method can achieve seawater electrolysis to produce hydrogen, the platinum-based noble metals in the platinum-carbon catalyst are costly and cannot be used on a large scale. Moreover, the corrosion of chloride ions and the deposition of metal cations in the complex seawater will deactivate it, hindering the development of the electrolysis of seawater to produce hydrogen technology. Therefore, designing a high-performance, low-cost, and corrosion-resistant electrocatalyst has become one of the key issues in the development of seawater electrolysis technology. Summary of the Invention

[0005] In order to overcome the above problems, the present invention provides an electrocatalyst for seawater electrolysis to produce hydrogen, a preparation method thereof, and an application thereof.

[0006] To achieve the above technical objectives, the present invention adopts the following technical solutions:

[0007] In the first aspect of the present invention, there is provided an electrocatalyst for seawater electrolysis to produce hydrogen, wherein the electrocatalyst uses titanium carbide nanofibers as a carrier and is loaded with ruthenium nanoparticles.

[0008] In the second aspect of the present invention, there is provided a preparation method of the above electrocatalyst for seawater electrolysis to produce hydrogen, including:

[0009] (1) Dissolving a carbon source and a titanium source in a solvent to form a spinning dope, preparing it into a nanofiber membrane by electrospinning method, and performing a carbothermal reduction reaction after pre-oxidation to obtain titanium carbide nanofibers;

[0010] (2) The ruthenium nanoparticles are loaded on titanium carbide nanofibers by rapid Joule heat treatment to obtain the electrocatalyst Ru@TiC.

[0011] In the third aspect of the present invention, there is provided an application of the above-mentioned electrocatalyst for hydrogen production by seawater electrolysis in hydrogen production by seawater electrolysis.

[0012] The beneficial effects of the present invention are as follows:

[0013] (1) The electronic structure of metallic ruthenium is similar to that of platinum, and it also has good catalytic effects on the electrocatalytic hydrogen evolution reaction. Moreover, its price is lower. However, ruthenium nanoparticles tend to agglomerate, which limits their application in electrocatalytic hydrogen evolution. In the present invention, titanium carbide nanofibers are obtained by electrospinning. This nanofiber not only has a large specific surface area, which is conducive to the loading of ruthenium nanoparticles; at the same time, there is a metal-support interaction between ruthenium and the carbide, which can stabilize the loaded ruthenium nanoparticles and solve the problem of easy agglomeration of ruthenium nanoparticles; the formed electrocatalyst Ru@TiC has a larger specific surface area of chemical reaction activity and richer active sites of chemical reaction, making this catalyst have higher catalytic reaction activity. Furthermore, titanium carbide, as a titanium-based compound, is a "transition metal interstitial compound" formed by carbon atoms incorporated into the lattice of the parent titanium, and it has good electrical conductivity and corrosion resistance. Good electrical conductivity can increase the electrocatalytic effect.

[0014] (2) The electrocatalyst Ru@TiC provided by the present invention can be applied to hydrogen production by electrolyzing seawater under acidic conditions or alkaline conditions due to its good corrosion resistance, catalytic activity and electrical conductivity.

[0015] (3) The electrocatalyst Ru@TiC provided by the present invention can carry out electrocatalytic hydrogen production in acidic fresh water, alkaline fresh water, acidic seawater and alkaline seawater, and all have good catalytic activity and stability.

[0016] (4) The electrocatalyst Ru@TiC provided by the present invention has a simple preparation process, is economical and practical, does not require special equipment and harsh conditions, has practical value, and is easy to scale up production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The attached drawings forming a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention.

[0018] Figure 1 It is a scanning electron microscope image of the titanium carbide nanofibers prepared in Example 1 of the present invention, where a and b are the results taken at different magnification multiples;

[0019] Figure 2 is the X-ray diffraction pattern of the titanium carbide nanofibers prepared in Example 1 of the present invention;

[0020] Figure 3 is the transmission electron microscopy image of the Ru@TiC electrocatalyst prepared in Example 3 of the present invention, where a and b are the results taken at different magnifications;

[0021] Figure 4 is the cyclic performance test result of the Ru@TiC electrocatalyst obtained in Example 3 of the present invention for hydrogen evolution reaction by electrolyzing water in an acidic environment;

[0022] Figure 5 is the cyclic performance test result of the Ru@TiC electrocatalyst obtained in Example 3 of the present invention for hydrogen evolution reaction by electrolyzing water under acidic natural seawater conditions;

[0023] Figure 6 is the cyclic performance test result of the Ru@TiC electrocatalyst obtained in Example 3 of the present invention for hydrogen evolution reaction by electrolyzing water in an alkaline environment;

[0024] Figure 7 is the cyclic performance test result of the Ru@TiC electrocatalyst obtained in Example 3 of the present invention for hydrogen evolution reaction by electrolyzing water under alkaline natural seawater conditions;

[0025] Figure 8 is the chronopotentiometry test result of the Ru@TiC electrocatalyst obtained in Example 3 of the present invention for hydrogen evolution reaction by electrolyzing water in an alkaline saturated sodium chloride environment. Detailed Embodiments

[0026] It should be noted that the following detailed description is exemplary and is intended to provide further illustration of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0027] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0028] The first typical embodiment of the present invention provides an electrocatalyst for hydrogen production by electrolyzing seawater. The electrocatalyst uses titanium carbide nanofibers as a carrier and is loaded with ruthenium nanoparticles.

[0029] In one or more embodiments, the loading amount of ruthenium nanoparticles is 0.5% to 30 wt%.

[0030] A second exemplary embodiment of the present invention provides a method for preparing the above-described electrocatalyst for hydrogen production by seawater electrolysis, comprising:

[0031] (1) Dissolving a carbon source and a titanium source in a solvent to form a spinning dope, preparing it into a nanofiber membrane by electrospinning, and performing a carbothermal reduction reaction after pre-oxidation to obtain titanium carbide nanofibers;

[0032] (2) Loading ruthenium nanoparticles onto the titanium carbide nanofibers by rapid Joule heat treatment to obtain the electrocatalyst Ru@TiC.

[0033] In one or more embodiments, in step (1), the carbon source is a high molecular polymer;

[0034] Preferably, the high molecular polymer includes one or several of polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and polylactic acid (PLA).

[0035] In one or more embodiments, in step (1), the titanium source includes one of tetrabutyl titanate, tetraisopropyl titanate, or titanium tetrachloride.

[0036] In one or more embodiments, in step (1), the mass ratio of the carbon source to the titanium source is 0.25 to 3:1;

[0037] In one or more embodiments, in step (1), the solvent includes one or several of N,N-dimethylformamide, acetic acid, water, ethanol, or chloroform.

[0038] In one or more embodiments, in step (1), the concentration of the titanium source in the solvent is 0.5 to 3 mg / mL.

[0039] In one or more embodiments, in step (1), the process parameters of electrospinning are: the advancing speed of the spinning dope is 0.5 to 2 mL / h, preferably 1 mL / h; the receiving distance is 8 to 30 cm, preferably 15 to 22 cm, more preferably 18 cm; the voltage is 8 to 30 kV, preferably 14 to 30 kV, more preferably 16 kV; the spinning time is 2 to 50 h, preferably 8 to 12 h, more preferably 10 h.

[0040] In one or more embodiments, in step (1), the pre-oxidation is to anneal the nanofiber membrane by heating under air or oxygen conditions, with the temperature being 100 - 280°C, preferably 200 - 280°C, and more preferably 260°C; the holding time is 0.5 - 20 h, preferably 0.5 - 5 h, and more preferably 2 h; the heating rate is 5 - 20°C / min.

[0041] In one or more embodiments, in step (1), the carbothermal reduction reaction is high-temperature calcination, with the calcination temperature being 1400 - 2200°C, preferably 1400 - 1600°C, and more preferably 1500°C; the calcination time is 1 - 12 h, preferably 1 - 5 h, and more preferably 2 h; the heating rate is 5 - 20°C / min.

[0042] In one or more embodiments, in step (1), the width of the obtained titanium carbide nanofibers is 100 - 1000 nm.

[0043] In one or more embodiments, in step (2), the method of loading ruthenium nanoparticles onto titanium carbide nanofibers by rapid Joule heat treatment includes:

[0044] Dropwise coat a ruthenium salt solution onto the titanium carbide nanofibers, and place it in a Joule heat device for heating to obtain the electrocatalyst Ru@TiC.

[0045] Preferably, the solute ruthenium salt in the ruthenium salt solution drop includes one of ruthenium chloride or ruthenium acetylacetonate;

[0046] Preferably, the solvent in the ruthenium salt solution drop includes one of water, methanol, ethanol, or N,N-dimethylformamide.

[0047] Preferably, the temperature set for heating in the Joule heat device is 400 - 2200°C; the Joule heat process can be repeated 1 - 10 times, and the heating time for each time is 4 - 6 s.

[0048] The third typical embodiment of the present invention provides the application of the above electrocatalyst for hydrogen production by seawater electrolysis in hydrogen production by seawater electrolysis.

[0049] In one or more embodiments, the pH value of seawater is adjusted to 0 - 3 and / or 12 - 14. Seawater can be in either acidic or alkaline conditions.

[0050] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with specific examples.

[0051] Example 1

[0052] Prepare a polymer fiber membrane using the electrospinning method as follows:

[0053] Dissolve polyacrylonitrile (1.0 g) and tetrabutyl titanate (2 mL) in a mixed solution of N,N-dimethylformamide (9 mL) and acetic acid (1 mL), stir evenly to form a yellow transparent solution, and reserve it as the spinning dope;

[0054] Use electrospinning method to prepare a fiber membrane from the spinning dope. The electrospinning high voltage is 16 kV, the distance between the tip part of electrospinning and the wire collecting device (receiving distance) is 18 cm, the electrospinning time is 10 h, and the advancing speed of the spinning dope is 1 mL / h. After electrospinning, a white polymer membrane is formed. Put the polymer membrane into an oven at 60 °C and dry it overnight to remove the residual solvent, and finally obtain a uniform and soft polymer fiber membrane.

[0055] The pre-oxidation process is carried out under air conditions, with a heating rate of 5 °C / min, a temperature of 260 °C, and a holding time of 2 h; the carbonization process is carried out in an inert gas argon atmosphere, with a heating rate of 5 °C / min, a temperature of 1500 °C, and a time of 2 h, and then a one-dimensional titanium carbide nanofiber material (TiC) is obtained. Electrospinning technology is an effective method for preparing one-dimensional nanofibers. It can accurately control the fiber diameter, ensure the uniformity and controllability of the fibers, and the intertwined one-dimensional interconnected structure is conducive to the formation of a conductive network, making its carbonized product have good electrical conductivity and is conducive to the progress of the electrocatalytic reaction. This method is simple to operate, has a low equipment cost, and can easily adjust the composition and structure of the fibers, which is conducive to the preparation and popularization of materials.

[0056] The scanning electron microscope image of the titanium carbide material obtained in this example is as Figure 1 shown, and the X-ray diffraction result is as Figure 2 shown. Even after pre-oxidation and carbonization annealing treatment, the fiber morphology can still be maintained, and there is no obvious agglomeration, indicating that the carbide obtained by this treatment process is uniform and stable.

[0057] Example 2

[0058] Different from Example 1, dissolve polyvinylpyrrolidone (1 g) and titanium tetraisopropoxide (2 mL) in an ethanol solution, and the rest of the preparation processes and steps are the same as those in Example 1.

[0059] Example 3

[0060] Use the method of rapid Joule heat treatment to prepare a quantitatively controlled Ru@TiC electrocatalyst, specifically as follows:

[0061] Use the TiC obtained in Example 1 as the carrier, and cut the sintered TiC into about 0.5×1 cm 2The electrode; ruthenium chloride was prepared into an aqueous solution of ruthenium chloride at 10 mg / mL. 100 μL of the ruthenium chloride solution was taken and drop-coated on the TiC support. After drying with an infrared lamp, it was placed in a Joule-heating graphite boat. After three inert gas purges, a Joule-heating process treatment was carried out under vacuum conditions; the voltage and current output by the power supply were controlled to be 10 V and 25 A respectively, the temperature was about 1000 °C, heating was stopped within 4 s, and after cooling to room temperature, the Ru@TiC electrocatalyst was obtained. Through ICP testing, the content of Ru was shown to be about 3 wt.%.

[0062] The TEM of the Ru@TiC electrocatalyst is as Figure 3 shown. It can be found from Figure 3 that Ru is uniformly loaded on TiC in the form of small particles.

[0063] Example 4

[0064] Using the Ru@TiC electrocatalyst obtained in Example 3, an electrolytic water hydrogen production test was carried out. It was cut into an electrode with a size of 0.5×0.5 cm 2 . In the electrolytic cell, a standard three-electrode system was adopted, a carbon rod was used as the counter electrode, and a mercury / mercurous sulfate electrode was used as the reference electrode, and it was tested in a 0.5 M sulfuric acid solution.

[0065] Using an electrochemical workstation as the detection and recording device, linear sweep voltammetry was used to detect the material performance. The initial voltage was set to -0.5 V, the termination voltage was -1.6 V, and the sweep rate was 2 mV / s. The initial working curve was recorded. Then, cyclic voltammetry was used to detect and evaluate the stability of the material. In the above voltage range, it was carried out at a sweep rate of 100 mV / s. After the cycle ended, linear sweep voltammetry was used again to test and evaluate the reacted material, and the working curve was recorded. The results are as Figure 4 shown. Initially, the overpotential at 10 mA / cm 2 was only 25 mV, and the overpotential when the current density reached 1 A / cm 2 was only 290 mV; and after 3000 cycles of stability testing, the performance of the Ru@TiC electrocatalyst remained almost unchanged, indicating that the catalyst has good catalytic activity and stability in the electrocatalytic hydrogen production reaction under acidic conditions.

[0066] Example 5

[0067] The difference between this example and Example 4 is that the catalyst was tested in a 0.5 mM sulfuric acid solution. The catalyst still has good catalytic activity and stability in the electrocatalytic hydrogen production reaction under acidic conditions with a pH of 3.

[0068] Example 6

[0069] Different from Example 4, the electrocatalyst was tested in acidic natural seawater of 0.5 M sulfuric acid, and the rest of the preparation processes and steps were the same as those in Example 4. The results are as Figure 5 shown. After 3000 cycles of stability testing, even in the environment of acidic natural seawater, the performance of the Ru@TiC electrocatalyst remained almost unchanged, indicating that the catalyst has good catalytic activity and stability.

[0070] Example 7

[0071] Using the Ru@TiC electrocatalyst obtained in Example 3, hydrogen production by electrolyzing water was tested. It was cut into an electrode of 0.5×0.5 cm 2 . In the electrolytic cell, a standard three-electrode system was used, with a carbon rod as the counter electrode and a mercury / mercuric oxide electrode as the reference electrode, and it was tested in 1 M potassium hydroxide solution.

[0072] Using an electrochemical workstation as the detection and recording device, linear sweep voltammetry was used to detect the material performance. The initial voltage was set at -0.6 V, the termination voltage was -1.6 V, and the sweep rate was 2 mV / s. The initial working curve was recorded. Then, cyclic voltammetry was used to detect and evaluate the stability of the material. In the above voltage range, it was carried out at a sweep rate of 100 mV / s. After the cycle ended, linear sweep voltammetry was used again to test and evaluate the reacted material, and the working curve was recorded. The results are as Figure 6 shown. Initially, the overpotential at 10 mA / cm 2 was only 20 mV, and the overpotential when the current density reached 1 A / cm 2 was only 260 mV; and after 3000 cycles of stability testing, the performance of the Ru@TiC electrocatalyst remained almost unchanged, indicating that the catalyst has good catalytic activity and stability in the electrocatalytic hydrogen production reaction under alkaline conditions.

[0073] Example 8

[0074] The difference between this example and Example 7 is that the catalyst was tested in 0.01 M potassium hydroxide solution. The catalyst still has good catalytic activity and stability in the electrocatalytic hydrogen production reaction under alkaline conditions with a pH of 12.

[0075] Example 9

[0076] Different from Example 7, the electrocatalyst was tested in alkaline natural seawater of 1 M potassium hydroxide, and the rest of the preparation processes and steps were the same as those in Example 6. The results are as Figure 7As shown, after 3000 cycles of stability testing, even in the harsh environment of alkaline natural seawater, the performance of the Ru@TiC electrocatalyst remains almost unchanged, indicating that the catalyst has good catalytic activity and stability.

[0077] Example 10

[0078] Different from Example 7, the electrocatalyst was tested in a 1M potassium hydroxide solution containing saturated sodium chloride, and its stability was tested by chronopotentiometry. At a current density of 500 mA / cm 2 , during a hydrogen production reaction lasting up to 100 hours, the results are as Figure 8 shown, showing good stability, indicating that it still has good catalytic activity, stability, and excellent corrosion resistance in an extremely harsh saturated sodium chloride environment.

[0079] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An electrocatalyst for hydrogen production by seawater electrolysis, characterized in that, The electrocatalyst uses titanium carbide nanofibers as a carrier and is loaded with ruthenium nanoparticles; among them, the loading amount of ruthenium nanoparticles is 0.5% - 30 wt.%. A method for preparing an electrocatalyst, comprising: (1) Dissolving a carbon source and a titanium source in a solvent to form a spinning dope, preparing it into a nanofiber membrane by electrospinning, and performing a carbothermal reduction reaction after pre-oxidation to obtain titanium carbide nanofibers; The mass ratio of the carbon source to the titanium source is 0.25 - 3:1; The carbothermal reduction reaction is high-temperature calcination, the calcination temperature is 1400 - 2200 °C; the calcination time is 1 - 12 h; the heating rate is 5 - 20 °C / min; (2) Using the method of rapid Joule heat treatment to load ruthenium nanoparticles on titanium carbide nanofibers to obtain the electrocatalyst Ru@TiC; The specific method includes: Dropping a ruthenium salt solution onto titanium carbide nanofibers and heating it in a Joule heat device to obtain the electrocatalyst Ru@TiC; The solvent in the ruthenium salt solution drop includes one of water, methanol, ethanol or N,N-dimethylformamide.

2. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, wherein In step (1), the carbon source is a polymer.

3. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 2, characterized in that, In step (1), the polymer includes one or several of polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and polylactic acid (PLA); Or, in step (1), the titanium source includes one of tetrabutyl titanate, tetraisopropyl titanate or titanium tetrachloride; Or, in step (1), the solvent includes one or several of N,N-dimethylformamide, acetic acid, water, ethanol or chloroform; Or, in step (1), the concentration of the titanium source in the solvent is 0.5 - 3 mg / mL.

4. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that, In step (1), the process parameters of electrospinning are: the advancing speed of the spinning dope is 0.5 - 2 mL / h; the receiving distance is 8 - 30 cm; the voltage is 8 - 30 kV; the spinning time is 2 - 50 h.

5. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, wherein, In step (1), the process parameters of electrospinning are: the advancing speed of the spinning dope is 1 mL / h; the receiving distance is 15 - 22 cm; the voltage is 14 - 30 kV; the spinning time is 8 - 12 h.

6. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, wherein In step (1), the process parameters of electrospinning are: the receiving distance of the spinning dope is 18 cm; the voltage is 16 kV; the spinning time is 10 h.

7. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that, In step (1), pre-oxidation is to perform temperature-rising annealing on the nanofiber membrane under air or oxygen conditions, the temperature is 100 - 280 °C; the holding time is 0.5 - 20 h; the heating rate is 5 - 20 °C / min.

8. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that, In step (1), pre-oxidation is to perform temperature-rising annealing on the nanofiber membrane under air or oxygen conditions, the temperature is 200 - 280 °C; the holding time is 0.5 - 5 h.

9. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that, In step (1), pre-oxidation is to perform temperature-rising annealing on the nanofiber membrane under air or oxygen conditions, the temperature is 260 °C; the holding time is 2 h.

10. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that, The width of the titanium carbide nanofibers is 100 - 1000 nm.

11. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that, In step (1), the carbothermal reduction reaction is high-temperature calcination, the calcination temperature is 1400 - 1600 °C; the calcination time is 1 - 5 h.

12. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, wherein In step (1), the carbothermal reduction reaction is high-temperature calcination, the calcination temperature is 1500 °C, and the calcination time is 2 h.

13. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that, In step (2), the solute ruthenium salt in the ruthenium salt solution drop includes one of ruthenium chloride or ruthenium acetylacetonate.

14. The electrocatalyst for hydrogen production by seawater electrolysis according to claim 1, wherein, In step (2), the temperature set by the Joule heating device is 400 - 2200 °C; the Joule heating process can be repeated 1 - 10 times, and the heating time for each time is 4 - 6 s.

15. Application of the electrocatalyst for seawater electrolysis hydrogen production according to any one of claims 1 - 14 in seawater electrolysis hydrogen production.

16. The application according to claim 15, wherein The pH value of seawater is 0 - 3 and / or 12 - 14.

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