Ru-based monatomic alloy electrocatalyst, preparation method and application thereof
By anchoring transition metal single atoms to Ru nanocrystals on carbon fiber paper, Ru-based single-atom alloy electrocatalysts were prepared, solving the kinetic and stability problems of hydrogen evolution reaction under high current density and achieving high efficiency in hydrogen evolution performance and mechanical stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- TAIYUAN UNIVERSITY OF TECHNOLOGY
- Filing Date
- 2023-03-29
- Publication Date
- 2026-05-29
AI Technical Summary
Existing technologies struggle to achieve rapid hydrogen evolution reaction kinetics and mechanical stability at high current densities, especially under alkaline conditions. The lack of regulation and persistence of active sites in transition metal single-atom catalysts limits their large-scale application.
A Ru-based single-atom alloy electrocatalyst was prepared by anchoring transition metal single atoms and coupling them with ultra-small Ru nanocrystals on carbon fiber paper. The preparation process included pre-activated carbon paper and pulse electrodeposition.
This study achieved a long-term stable hydrogen evolution reaction under high current density, exposed more active sites, regulated the electronic structure of Ru nanocrystals, simplified the preparation process, and has the potential for large-scale production.
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Figure CN116536697B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of high-current water electrolysis for hydrogen production technology, specifically to a Ru-based single-atom alloy electrocatalyst, its preparation method, and its application. Background Technology
[0002] Hydrogen energy, with its high calorific value and pollution-free combustion products, has become an important representative of energy conservation and emission reduction, as exemplified by the application of hydrogen fuel cell vehicles. Electrochemical water splitting can produce hydrogen through the hydrogen evolution reaction (HER) at the cathode, and due to its green and sustainable nature, it is considered a reliable route. However, compared to the direct production of hydrogen from protons under acidic conditions, the HER requires an additional water splitting process in a strongly alkaline environment, limiting the kinetics of the HER. Although some progress has been made in the exploration of such catalysts, many challenges remain in achieving a fully economical hydrogen economy. In fact, industrial-scale water electrolysis must undergo demanding conditions, including rapid charge transfer at high current densities, superior mechanical stability, bubble kinetics, and the adsorption or covering of intermediates. Therefore, achieving rapid HER kinetics and superior mechanical stability at high current densities is challenging but crucial for realizing industrial hydrogen production.
[0003] Platinum (Pt)-based catalysts are considered to have optimal reaction kinetics for improving HER kinetics, but their scarcity and high cost limit their large-scale application. Transition metals, represented by nickel (Ni), hold promise as economical alternatives to Pt catalysts for HER. To date, various types and sizes of transition metal materials (nanoparticles, nanoclusters, and single atoms) have been extensively studied as potential electrocatalysts for HER. Indeed, scaling down is an effective way to tune the performance of functional materials, as smaller catalysts can provide more active sites, such as transition metal single atoms with unique electronic properties. However, the characteristics of their individual sites, their persistence under alkaline conditions, and the limitations on the general tuning of active sites hinder their large-scale application, especially at high current densities where the requirements for the comparability and mechanical stability of active sites are more stringent. From this perspective, the rational application of single-atom catalysts for HER at high current densities remains extremely challenging, but also crucial.
[0004] Ruthenium (Ru), a relatively inexpensive platinum-like metal, is considered a potential hydrogen evolution catalyst due to its similar hydrogen bonding strength to that of Pt. To our knowledge, modifying the chemical environment of Ru by establishing heteroatom bonds or alloying more readily modulates its chemical and electronic properties, which is more favorable for hydrogen evolution reaction (HER). Indeed, the inherently strong binding energy of Ru-H promotes efficient H adsorption, but the strong adsorption of Ru by the OH(H) intermediate usually leads to the covering of active Ru, thus hindering water re-adsorption. More importantly, there are few reports on the modulation of the Ru-OH adsorption energy in basic HER kinetics. Therefore, it is feasible to modulate the adsorption environment of Ru by introducing transition metal single atoms, a strategy that further ensures the durability of single atoms under high currents. Summary of the Invention
[0005] This invention overcomes the shortcomings of the prior art and provides a Ru-based single-atom alloy electrocatalyst.
[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: a Ru-based single-atom alloy electrocatalyst, which uses pre-activated carbon fiber paper as a substrate, and anchors transition metal single atoms on the carbon substrate through one-step pulse electrodeposition, and couples this transition metal single-atom anchored carbon structure with ultra-small Ru nanocrystals to obtain the Ru-based single-atom alloy electrocatalyst.
[0007] The present invention also provides a method for preparing the above-mentioned Ru-based single-atom alloy electrocatalyst, comprising the following steps:
[0008] (1) Soak the clean carbon paper in HNO3 solution for 30 min, then rinse it with water and ethanol; after drying, the carbon paper is subjected to 5 cycles of voltammetry in H2SO4 solution, then rinsed with water and ethanol, and vacuum dried to obtain pre-activated carbon paper.
[0009] (2) Using the pre-activated carbon paper obtained in step (1) as the working electrode, a solution containing ruthenium chloride (RuCl3·xH2O), transition metal ion salt, boric acid, polyvinylpyrrolidone and ammonium chloride was prepared. The pH of the solution was adjusted to 2.7 with ammonia water, and a pulse voltage was applied for in-situ electrodeposition for 8000 s. The obtained catalyst was washed several times with deionized water and ethanol, and then dried under vacuum to obtain Ru-based single-atom alloy electrocatalyst.
[0010] Furthermore, in step (1), the concentration of the HNO3 solution is 1.0 M and the concentration of the H2SO4 solution is 0.5 M.
[0011] Furthermore, the transition metal ion salt mentioned in step (2) is one of the soluble Ni, Co, Fe, Mn, Cr, Cu and Zn salts, with a concentration of 150 mmol / L.
[0012] Furthermore, the molar ratio of ruthenium metal and transition metal salt in step (2) is 1:150.
[0013] Furthermore, in step (2), the mass fraction of ammonia is 25%, the concentration of boric acid in the solution is 160 mmol / L, the concentration of ammonium chloride is 100 mmol / L, and the concentration of polyvinylpyrrolidone is 0.01 g / mL.
[0014] Furthermore, the pulse electrodeposition in step (2) is a unipolar pulse deposition, the potential of which is -1.5 V to -0.8 V vs. Ag / AgCl, and the silver / silver chloride electrode is the reference electrode; the pulse interval of the unipolar pulse deposition is 1 s.
[0015] In addition, the present invention also provides the application of the above-mentioned Ru-based single-atom alloy electrocatalyst in high-current water electrolysis for hydrogen evolution.
[0016] The Ru-based single-atom alloy catalyst described in this invention is based on the requirement of hydrogen evolution through high-current water electrolysis. It is a structure of transition metal single atom-carbon modified ultra-small Ru nanocrystals, which not only stabilizes and protects the transition metal single atom, but also ensures continuous and rapid hydrogen evolution under high current through the coupling of the single atom and the Ru ultra-small nanocrystals.
[0017] Compared with the prior art, the present invention has the following beneficial effects:
[0018] 1. The preparation process of this invention is simple, easy to operate, and can achieve rapid large-scale production.
[0019] 2. The Ru-based single-atom alloy catalyst prepared by this invention has an ultra-low Ru nanoparticle size (~2 nm), which can expose more active sites, and the special electronic properties of transition metal single atoms can achieve the regulation of the electronic structure and adsorption energy of Ru nanocrystals.
[0020] 3. The Ru-based single-atom alloy prepared by this invention has an ultra-low hydrogen evolution overpotential and can achieve long-term stable hydrogen evolution under high current density.
[0021] 4. The present invention is reasonably designed and has a simple process. It can introduce different transition metal single atoms and has great application prospects. Attached Figure Description
[0022] Figure 1 The RuNi prepared in Example 1 of this invention SAs Scanning electron microscope image of the electrocatalyst (Ni single-atom modified Ru nanocrystals).
[0023] Figure 2 The RuNi prepared in Example 1 of this invention SAs Transmission electron microscope image of an electrocatalyst.
[0024] Figure 3 The RuNi prepared in Example 1 of this invention SAs Aberration-corrected electron micrograph of an electrocatalyst.
[0025] Figure 4 The RuNi prepared in Example 1 of this invention SAs X-ray diffraction pattern of the electrocatalyst.
[0026] Figure 5 The RuNi prepared in Example 1 of this invention SAs Raman spectrum of an electrocatalyst.
[0027] Figure 6 The RuNi prepared in Example 1 of this invention SAs X-ray absorption near-edge structure of electrocatalyst.
[0028] Figure 7 The RuNi prepared in Example 1 of this invention SAs Polarization curve of hydrogen evolution reaction of electrocatalyst (1 mol / L KOH solution).
[0029] Figure 8 The RuNi prepared in Example 1 of this invention SAs Hydrogen evolution stability test curve of electrocatalyst.
[0030] Figure 9 RuCo prepared in Example 2 of this invention SAs Polarization curves of the electrocatalyst in 1.0 mol / L KOH for hydrogen evolution performance testing.
[0031] Figure 10 RuFe prepared in Example 3 of this invention SAs Polarization curves of the electrocatalyst in 1.0 mol / L KOH for hydrogen evolution performance testing.
[0032] Figure 11 RuMn prepared in Example 4 of this invention SAs Polarization curves of the electrocatalyst in 1.0 mol / L KOH for hydrogen evolution performance testing.
[0033] Figure 12 RuCu prepared in Example 5 of this invention SAs Polarization curves of the electrocatalyst in 1.0 mol / L KOH for hydrogen evolution performance testing.
[0034] Figure 13 RuCr prepared in Example 6 of this invention SAs Polarization curves of the electrocatalyst in 1.0 mol / L KOH for hydrogen evolution performance testing.
[0035] Figure 14 RuZn prepared in Example 7 of this invention SAs Polarization curves of the electrocatalyst in 1.0 mol / L KOH for hydrogen evolution performance testing. Detailed Implementation
[0036] The present invention will be further described below with reference to specific embodiments. Example 1
[0037] A Ru-based single-atom alloy electrocatalyst for high-current water electrolysis and hydrogen evolution includes the following steps:
[0038] (1) Soak the clean carbon paper in 1.0 M HNO3 solution for 30 min, and then activate it in 0.5 M H2SO4 solution for 5 cycles of voltammetry to obtain pre-activated carbon paper.
[0039] (2) Prepare 100 mL of a solution containing 0.5 mmol / L ruthenium chloride (RuCl3·xH2O), 150 mmol / L nickel chloride (NiCl2·6H2O), 160 mmol / L boric acid, 100 mmol / L ammonium chloride, and 1.0 g polyvinylpyrrolidone. Adjust the pH of the solution to 2.7 with 25% ammonia. Using the pre-activated carbon paper from step (1) as the working electrode, a silver / silver chloride electrode as the reference electrode, and a platinum column as the working electrode, perform in-situ electrodeposition for 8000 s using a monopolar pulse technique on an electrochemical workstation. The deposition potential is -0.8 V vs. Ag / AgCl. The obtained catalyst is washed several times with deionized water and ethanol, and then vacuum dried to obtain RuNi. SAs Electrocatalyst.
[0040] Figure 1 It is RuNi SAs Scanning electron microscope images of electrocatalysts, from Figure 1 As can be seen, the material prepared by in-situ electrodeposition has a cauliflower-like morphology composed of small, rough-surfaced particle clusters, with the large cauliflower-like particles having a diameter of about 1 μm.
[0041] Figure 2 It is RuNi SAs Transmission electron microscopy images of the catalyst, from Figure 2 It can be seen that the particle size of Ru nanocrystals is about 2 nm. The ultra-small size of Ru nanocrystals can provide a larger active area and expose more active sites.
[0042] Figure 3 It is RuNi SAs Aberration-corrected electron micrographs of the catalyst, from Figure 3It can be seen that Ni elements are dispersed in the form of single atoms as bright spots and Ru crystals are uniformly dispersed. Furthermore, the aberration elemental scanning results further confirm the dispersion positions of Ni single atoms and Ru nanocrystals.
[0043] Figure 4 It is RuNi SAs The X-ray diffraction pattern of the catalyst, by Figure 4 It can be seen that its diffraction peaks correspond to the characteristic peaks of the substrate carbon paper and Ru nanocrystals, respectively, indicating the successful loading of Ru nanocrystals. Furthermore, the broad diffraction peaks of Ru nanocrystals further confirm the small particle size of the material.
[0044] Figure 5 It is blank carbon paper and RuNi SAs Raman spectra of the catalyst, from Figure 3 It can be seen that blank carbon paper and RuNi SAs Catalyst at 1350 cm -1 (D peak) and 1582cm -1 (G peak) exhibits the characteristic signal peak of carbon materials, and compared with blank carbon paper, RuNi SAs The significantly enhanced D / G peak intensities of the catalyst indicate that the RuNi was loaded by unipolar pulse deposition. SAs The degree of carbon defects on the surface of the carbon paper is enhanced after catalysis, and carbon defects are often more conducive to the anchoring of single atoms.
[0045] Figure 6 It is RuNi SAs The near-edge structure of Ni element X-ray absorption in the catalyst. From Figure 6 The results show that no obvious metallic bonding peaks were found at 2-3 Å, confirming that Ni exists in the form of single atoms, and a bonding peak at 1.8 Å proves that Ni is anchored on the carbon paper.
[0046] Figure 7 It is RuNi SAs The hydrogen evolution reaction polarization curve of the catalyst (1 mol / L KOH solution) is derived from... Figure 7 It is evident that this electrode can undergo hydrogen evolution reaction at ultra-low overpotentials, specifically at -10 mA cm⁻¹. -2 and -1000 mA cm -2 The hydrogen evolution overpotentials at current densities are 9 mV and 253 mV, respectively, which fully demonstrates that the material has excellent hydrogen evolution activity under high current.
[0047] Figure 8 It is RuNi SAs Hydrogen evolution stability test curves of the catalyst. As shown in the figure, this material exhibits stability at low currents (-10 mA / cm²). -2 ) and high current (-3000 mA cm) -2Under the conditions of 200 h (100 h), there was no significant decay, indicating that the material exhibits excellent high-current hydrogen evolution stability under long-term strong alkaline conditions. Example 2
[0048] A Ru-based single-atom alloy electrocatalyst for high-current water electrolysis and hydrogen evolution includes the following steps:
[0049] (1) Soak the clean carbon paper in 1.0 M HNO3 solution for 30 min, and then activate it in 0.5 M H2SO4 solution for 5 cycles of voltammetry to obtain pre-activated carbon paper.
[0050] (2) Prepare 100 mL of a solution containing 0.5 mmol / L ruthenium chloride (RuCl3·xH2O), 150 mmol / L cobalt chloride (CoCl2·6H2O), 160 mmol / L boric acid, 100 mmol / L ammonium chloride, and 1.0 g polyvinylpyrrolidone. Adjust the pH of the solution to 2.7 with 25% ammonia. Using the pre-activated carbon paper from step (1) as the working electrode, a silver / silver chloride electrode as the reference electrode, and a platinum column as the working electrode, perform in-situ electrodeposition for 8000 s using a unipolar pulse method on an electrochemical workstation. The deposition potential is -1.0 V vs. Ag / AgCl. The obtained catalyst is washed several times with deionized water and ethanol, and then vacuum dried to obtain a Co single-atom modified Ru nanocrystalline electrocatalyst (denoted as RuCo). SAs ).
[0051] The RuCo prepared in Example 2 SAs The polarization curves for the hydrogen evolution performance test of the electrocatalyst in 1.0 mol / L KOH are shown below. Figure 9 As shown, by Figure 9 It can be seen that the prepared RuCo SAs Electrocatalyst at -10 mA cm -2 and -1000 mA cm -2 The hydrogen evolution overpotentials at the current densities are 40 mV and 452 mV, respectively. Example 3
[0052] A Ru-based single-atom alloy electrocatalyst for high-current water electrolysis and hydrogen evolution includes the following steps:
[0053] (1) Soak the clean carbon paper in 1.0 M HNO3 solution for 30 min, and then activate it in 0.5 M H2SO4 solution for 5 cycles of voltammetry to obtain pre-activated carbon paper.
[0054] (2) Prepare 100 mL of a solution containing 0.5 mmol / L ruthenium chloride (RuCl3·xH2O), 150 mmol / L ferric chloride (FeCl3·6H2O), 160 mmol / L boric acid, 100 mmol / L ammonium chloride, and 1.0 g polyvinylpyrrolidone. Adjust the pH of the solution to 2.7 with 25% ammonia. Using the pre-activated carbon paper from step (1) as the working electrode, a silver / silver chloride electrode as the reference electrode, and a platinum column as the working electrode, perform in-situ electrodeposition for 8000 s using a unipolar pulse method on an electrochemical workstation. The deposition potential is -1.0 V vs. Ag / AgCl. The obtained catalyst is washed several times with deionized water and ethanol, and then vacuum dried to obtain a Fe single-atom modified Ru nanocrystalline electrocatalyst (denoted as RuFe). SAs ).
[0055] RuFe prepared in Example 3 SAs The polarization curves for the hydrogen evolution performance test of the electrocatalyst in 1.0 mol / L KOH are shown below. Figure 10 As shown, by Figure 10 It can be seen that the prepared RuFe SAs Electrocatalyst at -10 mA cm -2 and -1000 mA cm -2 The hydrogen evolution overpotentials at the current densities are 19 mV and 230 mV, respectively. Example 4
[0056] A Ru-based single-atom alloy electrocatalyst for high-current water electrolysis and hydrogen evolution includes the following steps:
[0057] (1) Soak the clean carbon paper in 1.0 M HNO3 solution for 30 min, and then activate it in 0.5 M H2SO4 solution for 5 cycles of voltammetry to obtain pre-activated carbon paper.
[0058] (2) Prepare 100 mL of a solution containing 0.5 mmol / L ruthenium chloride (RuCl3·xH2O), 150 mmol / L manganese chloride (MnCl2·H2O), 160 mmol / L boric acid, 100 mmol / L ammonium chloride, and 1.0 g polyvinylpyrrolidone. Adjust the pH of the solution to 2.7 with 25% ammonia. Using the pre-activated carbon paper from step (1) as the working electrode, a silver / silver chloride electrode as the reference electrode, and a platinum column as the working electrode, perform in-situ electrodeposition for 8000 s using a unipolar pulse method on an electrochemical workstation. The deposition potential is -1.5 V vs. Ag / AgCl. The obtained catalyst is washed several times with deionized water and ethanol, and then vacuum dried to obtain a Ru nanocrystalline electrocatalyst modified with Mn single atoms (denoted as RuMn). SAs ).
[0059] RuMn prepared in Example 4 SAs The polarization curves for the hydrogen evolution performance test of the electrocatalyst in 1.0 mol / L KOH are shown below. Figure 11 As shown, by Figure 11 It can be seen that the prepared RuMn SAs Electrocatalyst - 10 mA cm -2 and -1000 mA cm -2 The hydrogen evolution overpotentials at the current densities are 31 mV and 348 mV, respectively. Example 5
[0060] A Ru-based single-atom alloy electrocatalyst for high-current water electrolysis and hydrogen evolution includes the following steps:
[0061] (1) Soak the clean carbon paper in 1.0 M HNO3 solution for 30 min, and then activate it in 0.5 M H2SO4 solution for 5 cycles of voltammetry to obtain pre-activated carbon paper.
[0062] (2) Prepare 100 mL of a solution containing 0.5 mmol / L ruthenium chloride (RuCl3·xH2O), 150 mmol / L copper nitrate (Cu(NO3)2·3H2O), 160 mmol / L boric acid, 100 mmol / L ammonium chloride, and 1.0 g polyvinylpyrrolidone. Adjust the pH of the solution to 2.7 with 25% ammonia. Using the pre-activated carbon paper from step (1) as the working electrode, a silver / silver chloride electrode as the reference electrode, and a platinum column as the working electrode, perform in-situ electrodeposition for 8000 s using a unipolar pulse method on an electrochemical workstation. The deposition potential is -1.0 V vs. Ag / AgCl. The obtained catalyst is washed several times with deionized water and ethanol, and then vacuum dried to obtain Cu single-atom modified Ru nanocrystalline electrocatalyst (denoted as RuCu). SAs ).
[0063] RuCu prepared in Example 5 SAs The polarization curves for the hydrogen evolution performance test of the electrocatalyst in 1.0 mol / L KOH are shown below. Figure 12 As shown, by Figure 12 It can be seen that the prepared RuCu SAs Electrocatalyst at -10 mA cm -2 and -1000 mA cm -2 The hydrogen evolution overpotentials at the current densities are 91 mV and 611 mV, respectively. Example 6
[0064] A Ru-based single-atom alloy electrocatalyst for high-current water electrolysis and hydrogen evolution includes the following steps:
[0065] (1) Soak the clean carbon paper in 1.0 M HNO3 solution for 30 min, and then activate it in 0.5 M H2SO4 solution for 5 cycles of voltammetry to obtain pre-activated carbon paper.
[0066] (2) Prepare 100 mL of a solution containing 0.5 mmol / L ruthenium chloride (RuCl3·xH2O), 150 mmol / L chromium chloride (CrCl3·6H2O), 160 mmol / L boric acid, 100 mmol / L ammonium chloride, and 1.0 g polyvinylpyrrolidone. Adjust the pH of the solution to 2.7 with 25% ammonia. Using the pre-activated carbon paper from step (1) as the working electrode, a silver / silver chloride electrode as the reference electrode, and a platinum column as the working electrode, perform in-situ electrodeposition for 8000 s using a unipolar pulse method on an electrochemical workstation. The deposition potential is -1.0 V vs. Ag / AgCl. The obtained catalyst is washed several times with deionized water and ethanol, and then vacuum dried to obtain a Cr single-atom modified Ru nanocrystalline electrocatalyst (denoted as RuCr). SAs ).
[0067] The RuCr prepared in Example 6 SAs The polarization curves for the hydrogen evolution performance test of the electrocatalyst in 1.0 mol / L KOH are shown below. Figure 13 As shown, by Figure 13 It can be seen that the prepared RuCr SAs Electrocatalyst at -10 mA cm -2 and -1000 mA cm -2 The hydrogen evolution overpotentials at the current densities are 27 mV and 377 mV, respectively. Example 7
[0068] A Ru-based single-atom alloy electrocatalyst for high-current water electrolysis and hydrogen evolution includes the following steps:
[0069] (1) Soak the clean carbon paper in 1.0 M HNO3 solution for 30 min, and then activate it in 0.5 M H2SO4 solution for 5 cycles of voltammetry to obtain pre-activated carbon paper.
[0070] (2) Prepare 100 mL of a solution containing 0.5 mmol / L ruthenium chloride (RuCl3·xH2O), 150 mmol / L zinc nitrate (Zn(NO3)2·6H2O), 160 mmol / L boric acid, 100 mmol / L ammonium chloride, and 1.0 g polyvinylpyrrolidone. Adjust the pH of the solution to 2.7 with 25% ammonia. Using the pre-activated carbon paper from step (1) as the working electrode, a silver / silver chloride electrode as the reference electrode, and a platinum column as the working electrode, perform in-situ electrodeposition for 8000 s using a unipolar pulse method on an electrochemical workstation. The deposition potential is -1.0 V vs. Ag / AgCl. The obtained catalyst is washed several times with deionized water and ethanol, and then vacuum dried to obtain a Zn single-atom modified Ru nanocrystalline electrocatalyst (denoted as RuZn). SAs ).
[0071] The RuZn prepared in Example 7 SAs The polarization curves for the hydrogen evolution performance test of the electrocatalyst in 1.0 mol / L KOH are shown below. Figure 14 As shown, by Figure 14 It can be seen that the prepared RuZn SAs Electrocatalyst at -10 mA cm -2 and -1000 mA cm -2 The hydrogen evolution overpotentials at the current densities are 40 mV and 350 mV, respectively.
[0072] Finally, it should be noted that the above embodiments describe the preferred specific measures of the present invention in detail. It should be understood that those skilled in the art can make many modifications and variations based on the concept of the present invention without creative effort. Therefore, any modifications or substitutions made by those skilled in the art based on the present invention and on the existing technology should be within the scope of protection defined by the claims.
Claims
1. A Ru-based single-atom alloy electrocatalyst, characterized in that, Using pre-activated carbon fiber paper as a substrate, transition metal single atoms are anchored onto the carbon substrate via unipolar pulse deposition. This transition metal single-atom-anchored carbon structure is then coupled with ultra-small Ru nanocrystals to obtain a Ru-based single-atom alloy electrocatalyst. The process includes the following steps: (1) Soak the clean carbon paper in HNO3 solution for 30 min, then rinse it with water and ethanol; after drying, the carbon paper is subjected to 5 cycles of voltammetry in H2SO4 solution, then rinsed with water and ethanol, and vacuum dried to obtain pre-activated carbon paper. (2) Using the pre-activated carbon paper obtained in step (1) as the working electrode, a solution containing ruthenium chloride, transition metal ion salt, boric acid, polyvinylpyrrolidone and ammonium chloride was prepared. The pH of the solution was adjusted to 2.7 with ammonia water. A unipolar pulse deposition was applied for 8000s. The resulting catalyst was washed several times with deionized water and ethanol. After vacuum drying, Ru-based single-atom alloy electrocatalyst was obtained.
2. The Ru-based single-atom alloy electrocatalyst according to claim 1, characterized in that, In step (1), the concentration of HNO3 solution is 1.0 M and the concentration of H2SO4 solution is 0.5 M.
3. The Ru-based single-atom alloy electrocatalyst according to claim 1, characterized in that, The transition metal ion salt mentioned in step (2) is one of the soluble Ni, Co, Fe, Mn, Cr, Cu and Zn salts, with a concentration of 150 mmol / L.
4. The Ru-based single-atom alloy electrocatalyst according to claim 1, characterized in that, The molar ratio of ruthenium chloride and transition metal ion salt in step (2) is 1:
150.
5. A Ru-based single-atom alloy electrocatalyst according to claim 1, characterized in that, The ammonia solution in step (2) has a mass fraction of 25%, the boric acid concentration in the solution is 160 mmol / L, the ammonium chloride concentration is 100 mmol / L, and the polyvinylpyrrolidone concentration is 0.01 g / mL.
6. The Ru-based single-atom alloy electrocatalyst according to claim 1, characterized in that, In step (2), the potential for unipolar pulse deposition is -1.5 V to -0.8 V vs. Ag / AgCl, and the silver / silver chloride electrode is the reference electrode; the pulse interval for unipolar pulse deposition is 1 s.
7. The application of the Ru-based single-atom alloy electrocatalyst as described in claim 1 in high-current water electrolysis for hydrogen evolution.