A high-activity anti-corrosion and anti-fouling nano-array material based on interface water regulation and a preparation method and application thereof

Abstract

The application belongs to the technical field of electrocatalytic materials, and particularly relates to a high-activity anti-corrosion and anti-fouling nano-array material based on interface water regulation and a preparation method and application thereof. The transition metal current collector is soaked in a solution containing a noble metal salt and a multi-functional organic molecule modifier, and is fully reacted to obtain the surface-modified transition metal hydroxide loaded noble metal nano-array material. For catalytic activity, the material can promote the hydrolysis of active hydrogen, and greatly improves the efficiency of seawater electrolysis hydrogen evolution. For material stability, in the complex environment of seawater, the material can not only effectively block the corrosion of corrosive ions in seawater to the substrate, prolonging the service life of the material, but also can inhibit the deposition of hydroxide scale layer on the electrode surface, effectively solving the performance degradation problem caused by fouling in seawater electrolysis hydrogen evolution. Thanks to the above excellent performance, the material of the application has great application potential in the field of seawater hydrogen production.

Description

Technical Field

[0001] This invention belongs to the field of electrocatalytic materials technology. More specifically, it relates to a highly active anti-corrosion and anti-fouling nanoarray material based on interfacial water regulation, its preparation method, and its application. Background Technology

[0002] Driven by dual carbon goals, large-scale hydrogen production has become a core task in the energy transition. Compared to traditional water electrolysis for hydrogen production, which relies on freshwater, seawater electrolysis for hydrogen production does not consume precious freshwater resources. It directly utilizes seawater, which accounts for 97% of the world's water resources, as a raw material, making it a truly feasible hydrogen production pathway for large-scale implementation. The hydrogen evolution reaction (HER) at the cathode is the core half-reaction in seawater electrolysis for hydrogen production, and its catalytic performance directly determines the efficiency and cost of hydrogen production, representing a key bottleneck restricting the industrial application of the technology.

[0003] Currently, noble metal-based catalysts (such as Pt and Pd) have long been considered the preferred choice for HER electrocatalysts due to their excellent intrinsic catalytic activity, with their hydrogen adsorption free energy approaching the theoretical optimum. However, in the complex seawater electrolysis environment, these catalysts face three major challenges: First, the high concentration of chloride ions in seawater directly corrodes the catalyst surface, leading to the destruction of its crystal structure and rapid loss of active sites; second, calcium and magnesium ions form hydroxide precipitates during electrolysis, adhering to the electrode surface and causing scaling, which obscures active sites and increases mass transfer resistance; third, the electronic structure of traditional noble metal catalysts is not well regulated, and the interfacial water structure is not optimized, resulting in a slow kinetic process for hydrogen production through hydrolysis, making them unsuitable for the complex reaction environment of seawater systems.

[0004] Therefore, developing novel noble metal-based materials with high catalytic activity, corrosion resistance, and scale resistance for seawater electrolysis systems has become crucial in the current field of hydrogen production from seawater electrolysis. Summary of the Invention

[0005] This invention addresses the problems of low catalytic activity, poor corrosion resistance, and poor scaling resistance in existing seawater electrolysis hydrogen production materials, and aims to provide a method for preparing surface-modified transition metal hydroxide-supported noble metal nanoarray materials.

[0006] A second objective of this invention is to provide a surface-modified transition metal hydroxide-supported noble metal nanoarray material prepared by the above-described preparation method.

[0007] A third objective of this invention is to provide the application of the above-mentioned surface-modified transition metal hydroxide-supported noble metal nanoarray materials in the electrolysis of seawater for hydrogen evolution.

[0008] The above-mentioned objective of this invention is achieved through the following technical solution:

[0009] This invention provides a method for preparing a surface-modified transition metal hydroxide-supported noble metal nanoarray material, comprising the following steps: The transition metal-based current collector was immersed in a solution containing noble metal salts and multifunctional organic molecular modifiers to carry out a solvothermal reaction. After post-treatment, the surface-modified transition metal hydroxide-supported noble metal nanoarray material was obtained. The multifunctional organic molecule modifier is selected from at least one of organic polycarboxylic acid compounds, organic polyphosphate compounds, and polyphenolic compounds.

[0010] This invention creatively discovers that using multifunctional organic molecular modifiers (organic polycarboxylic acids, organic polyphosphates, and polyphenols) to surface-modify transition metal hydroxide-supported noble metal nanoarray materials can simultaneously achieve three key performance breakthroughs: First, it optimizes the electronic structure of the material and effectively reduces the water dissociation energy barrier, promoting the efficient generation of active hydrogen and significantly enhancing the intrinsic catalytic activity of the material; second, it effectively repels corrosive ions (such as Cl-) in seawater through electrostatic repulsion. - This significantly improves the electrode's corrosion resistance; thirdly, multifunctional organic molecular modifiers can coordinate with calcium, magnesium, and other metal ions in seawater, reducing the corrosion resistance of the electrodes. 2+ Mg 2+ Plasma adsorption and deposition on the electrode surface inhibits the formation of precipitates such as hydroxides, significantly improving the material's anti-scaling performance. Compared to unmodified materials and commercial platinum-carbon electrodes, the material prepared in this invention exhibits significant advantages in catalytic activity, corrosion resistance, and anti-scaling stability. Among them, the material modified with organic polycarboxylic acid compounds shows the best performance: reaching 100 mA·cm⁻¹ in the hydrogen evolution reaction of seawater electrolysis. -2 The required potential is minimal (as low as -0.010 V), and it can operate stably for over 200 hours in simulated seawater electrolytes; even in electrolytes with a high risk of scaling (calcium and magnesium ion concentrations approximately 10 times that of real seawater), it can still operate stably for over 400 minutes. In summary, the material prepared in this invention provides core material support for the large-scale application of seawater hydrogen production technology.

[0011] Furthermore, the multifunctional organic molecule is an organic compound whose molecular structure contains two or more identical or different functional groups.

[0012] Furthermore, the organic polycarboxylic acid compounds are organic compounds containing two or more carboxyl (-COOH) functional groups in their molecules.

[0013] Furthermore, the organic polyphosphate compound contains two or more phosphate groups (-PO3H2, or its dissociated form -PO3H2) in its molecule. - -PO3 2-Organic compounds.

[0014] Furthermore, the polyphenolic compounds are organic compounds whose molecular structure contains two or more phenolic hydroxyl groups (-OH directly attached to the aromatic ring).

[0015] Preferably, the multifunctional organic molecule modifier is an organic polycarboxylic acid compound.

[0016] More preferably, the organic polycarboxylic acid compound is selected from at least one of 4,4'-biphenyldicarboxylic acid, 2-aminoterephthalic acid, isophthalic acid, and trimesic acid.

[0017] Preferably, the organopolyphosphoric acid compound is selected from zoledronic acid and / or aminotrimethylenephosphonic acid.

[0018] Preferably, the polyphenolic compound is selected from gallic acid and / or epigallocatechin gallate.

[0019] Preferably, the noble metal in the noble metal salt is selected from at least one of Pt, Ru, Pd, Ir, Os, Rh, Au, and Ag.

[0020] More preferably, the noble metal in the noble metal salt is selected from at least one of Pd, Ir, Rh, and Pt.

[0021] Preferably, the noble metal salt is selected from at least one of nitrates, acetates, chlorides, and acetylacetone salts.

[0022] Preferably, the concentration of the noble metal salt in the solution containing the noble metal salt and the multifunctional organic molecule modifier is 2.5~250 mmol / L, more preferably 5~150 mmol / L.

[0023] Preferably, the form of the transition metal current collector is selected from any one of metal foam, metal foil, metal plate, and metal mesh.

[0024] Preferably, the transition metal in the transition metal-based current collector is selected from at least one of Fe, Co, Ni, Cu, Ti, and Mo.

[0025] More preferably, the transition metal in the transition metal-based current collector is selected from at least one of Fe, Co, Ni, and Cu.

[0026] Optionally, the transition metal-based current collector is selected from any one of iron plate, copper mesh, nickel-iron alloy plate, and nickel-cobalt alloy plate.

[0027] Preferably, the solvent in the solution containing the noble metal salt and the multifunctional organic molecule modifier is selected from at least one of water, methanol, ethanol, ethylene glycol, isopropanol, acetone, N,N-dimethylformamide, and dimethyl sulfoxide.

[0028] More preferably, the solvent is selected from at least one of water, ethanol, ethylene glycol, and N,N-dimethylformamide.

[0029] Preferably, the volume ratio of the multifunctional organic molecule modifier to the solvent is 1:(0.5~150), more preferably 1:(1~100).

[0030] Preferably, the temperature of the solvothermal reaction is 25~200 ℃, more preferably 40~160 ℃.

[0031] Preferably, the solvothermal reaction time is 0.2 to 48 h, more preferably 1 to 40 h.

[0032] Preferably, the post-processing includes cooling, washing, and drying.

[0033] Optionally, the washing process involves washing with ethanol 1 to 5 times, specifically 3 times.

[0034] Optionally, the drying is performed at 40~80 ℃ for 8~16 h, specifically at 60 ℃ for 12 h.

[0035] The present invention also provides a surface-modified transition metal hydroxide-supported noble metal nanoarray material prepared by the preparation method described above.

[0036] The present invention also provides the application of the surface-modified transition metal hydroxide-supported noble metal nanoarray material in the hydrogen evolution reaction of water electrolysis.

[0037] Preferably, the hydrogen evolution reaction of water electrolysis is the hydrogen evolution reaction of seawater electrolysis.

[0038] The present invention has the following beneficial effects: This invention successfully addresses three major technical bottlenecks in the field of seawater electrolysis for hydrogen evolution—insufficient catalytic activity, easy electrode corrosion, and easy surface scaling—by introducing a multi-functional organic molecule modification strategy, achieving a comprehensive improvement in material performance. (1) Enhanced catalytic activity: Optimizing the electronic structure of the material significantly reduces the water dissociation energy barrier and promotes the efficient generation of active hydrogen. Compared with the unmodified material and commercial platinum-carbon electrodes, the modified material prepared in this invention exhibits superior catalytic activity in the electrolysis of seawater for hydrogen evolution.

[0039] (2) Improved corrosion resistance: Multifunctional organic molecules effectively block Cl in seawater through electrostatic repulsion.- The contact between corrosive ions and the electrode surface significantly improves the electrode's corrosion resistance.

[0040] (3) Improved anti-scaling stability: Multifunctional organic molecules can react with Ca in seawater 2+ Mg 2+ The metal ions form stable coordination chelates, which inhibit the formation of hydroxide scale.

[0041] Among them, the material modified with organic polycarboxylic acid compounds exhibits the best overall performance, reaching 100 mA·cm⁻¹ in the hydrogen evolution reaction of seawater electrolysis. -2 The minimum potential required for current density is as low as -0.010 V, and it can operate stably for more than 200 hours. In electrolytes with a high risk of scaling, where the calcium and magnesium ion concentration is 10 times that of real seawater, the modified electrode can operate stably for more than 400 minutes.

[0042] In summary, the surface-modified electrocatalytic material prepared by this invention provides core material support for the large-scale and long-term stable application of seawater hydrogen production technology, and has significant industrial application value. Attached Figure Description

[0043] Figure 1 The IP / Fe(OH) obtained in Example 1 x -SEM image of Pd@BPDC nanoarray material.

[0044] Figure 2 The IP / Fe(OH) obtained in Example 2 x -SEM image of Pd@ZA nanoarray material.

[0045] Figure 3 The IP / Fe(OH) obtained in Example 3 x -SEM image of Pd@GA nanoarray material.

[0046] Figure 4 The image shows a SEM image of the CuM / Cu(OH)2-Ir@ATA nanoarray material obtained in Example 4.

[0047] Figure 5 The image shows a SEM image of the CuM / Cu(OH)2-Ir@ZA nanoarray material obtained in Example 5.

[0048] Figure 6 The image shows a SEM image of the CuM / Cu(OH)2-Ir@GA nanoarray material obtained in Example 6.

[0049] Figure 7 The image shows a SEM image of the NIP / NiFe-OH-Rh@IPA nanoarray material obtained in Example 7.

[0050] Figure 8 The image shows a SEM image of the NIP / NiFe-OH-Rh@ATMP nanoarray material obtained in Example 8.

[0051] Figure 9 The image shows a SEM image of the NIP / NiFe-OH-Rh@EGCG nanoarray material obtained in Example 9.

[0052] Figure 10 This is a SEM image of the NCP / NiCo-OH-Pt@TMA nanoarray material obtained in Example 10.

[0053] Figure 11 The image shows the SEM image of the NCP / NiCo-OH-Pt@ATMP nanoarray material obtained in Example 11.

[0054] Figure 12 The LSV diagrams show the hydrogen evolution of seawater by electrocatalytic decomposition at room temperature using the materials obtained in Examples 1, 2, 3, and Comparative Example 1.

[0055] Figure 13 The graph shows the chlorine corrosion resistance test results of the materials obtained in Examples 1, 2, 3 and Comparative Example 1 during the electrocatalytic decomposition of seawater for hydrogen evolution at room temperature.

[0056] Figure 14 The graph shows the anti-scaling stability test results of the materials obtained in Examples 1, 2, 3 and Comparative Example 1 for the electrocatalytic decomposition of seawater into hydrogen at room temperature.

[0057] Figure 15 The LSV diagrams show the hydrogen evolution of seawater by electrocatalytic decomposition at room temperature using the materials obtained in Examples 4, 5, 6, and Comparative Example 2.

[0058] Figure 16 The graph shows the chlorine corrosion resistance test results of the materials obtained in Examples 4, 5, 6 and Comparative Example 2 during the electrocatalytic decomposition of seawater for hydrogen evolution at room temperature.

[0059] Figure 17 The graphs show the anti-scaling stability of the materials obtained in Examples 4, 5, 6 and Comparative Example 2 during the electrocatalytic decomposition of seawater for hydrogen evolution at room temperature.

[0060] Figure 18 The LSV diagrams show the hydrogen evolution of seawater by electrocatalytic decomposition at room temperature using the materials obtained in Examples 7, 8, 9 and Comparative Example 3.

[0061] Figure 19 The graph shows the chlorine corrosion resistance test results of the materials obtained in Examples 7, 8, 9 and Comparative Example 3 during the electrocatalytic decomposition of seawater for hydrogen evolution at room temperature.

[0062] Figure 20 The graph shows the anti-scaling stability test results of the materials obtained in Examples 7, 8, 9 and Comparative Example 3 for the electrocatalytic decomposition of seawater into hydrogen at room temperature.

[0063] Figure 21 The LSV diagrams show the hydrogen evolution of seawater by electrocatalytic decomposition at room temperature using the materials obtained in Examples 10, 11, and Comparative Example 4.

[0064] Figure 22 The graph shows the chlorine corrosion resistance test results of the materials obtained in Examples 10, 11 and Comparative Example 4 during the electrocatalytic decomposition of seawater for hydrogen evolution at room temperature.

[0065] Figure 23 The graph shows the anti-scaling stability test results of the materials obtained in Examples 10, 11 and Comparative Example 4 for electrocatalytic decomposition of seawater into hydrogen at room temperature. Detailed Implementation

[0066] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0067] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.

[0068] Example 1 IP / Fe(OH) x -Pd@BPDC nanoarray materials The IP / Fe(OH) x -Pd@BPDC (due to the Fe(OH) prepared in this invention) x Fe exhibits both +2 and +3 valence states, therefore a variable subscript x is used, where x ranges from 2 to x ≤ 3. Other similar expressions in this specification follow the same principle. The preparation method of the nanoarray material includes the following steps: (1) Dissolve 0.440 g (2.0 mmol) of palladium acetate (Pd(CH3CO2)2) in 20 mL of a prepared 4,4'-biphenyl dicarboxylic acid (BPDC)-N,N-dimethylformamide solution (volume ratio 1:100), and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm iron plates (IP) that have been washed clean are immersed in the mixed solution obtained in step (1) and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor is placed in a forced-air drying oven for a one-pot solvothermal reaction at 80 °C for 1 h. After the reaction is completed, the reactor is allowed to cool naturally. The cooled material is washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain Fe(OH) loaded on the IP current collector. x -Pd@BPDC nanoarray material (IP / Fe(OH)) x -Pd@BPDC).

[0069] The morphology of the obtained product was characterized using scanning electron microscopy (SEM). Figure 1 As can be seen from the figure, there is a uniformly distributed nanosheet structure on the IP current collector.

[0070] Example 2 IP / Fe(OH) x -Pd@ZA nanoarray materials Same as Example 1, except that 4,4'-biphenyl dicarboxylic acid (BPDC) is replaced with an equal volume of zoledronic acid (ZA), and the IP / Fe(OH) x The preparation method of Pd@ZA nanoarray material includes the following steps: (1) Dissolve 0.440 g (2.0 mmol) of palladium acetate (Pd(CH3CO2)2) in 20 mL of prepared zoledronic acid (ZA)-N,N-dimethylformamide solution (volume ratio 1:100) and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm iron plates (IP) that have been washed clean are immersed in the mixed solution obtained in step (1) and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor is placed in a forced-air drying oven for a one-pot solvothermal reaction at 80 °C for 1 h. After the reaction is completed, the reactor is allowed to cool naturally. The cooled material is washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain Fe(OH) loaded on the IP current collector. x -Pd@ZA nanoarray material (IP / Fe(OH)) x -Pd@ZA).

[0071] The material morphology of the obtained product was characterized using SEM. Figure 2 As can be seen from the figure, there is a uniformly distributed nanosheet structure on the IP current collector.

[0072] Example 3 IP / Fe(OH) x -Pd@GA nanoarray materials Same as Example 1, except that 4,4'-biphenyl dicarboxylic acid (BPDC) is replaced with an equal volume of gallic acid (GA), and the IP / Fe(OH) ratio is... x The preparation method of Pd@GA nanoarray material includes the following steps: (1) Dissolve 0.440 g (2.0 mmol) of palladium acetate (Pd(CH3CO2)2) in 20 mL of prepared gallic acid (GA)-N,N-dimethylformamide solution (volume ratio 1:100) and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm iron plates (IP) that have been washed clean are immersed in the mixed solution obtained in step (1) and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor is placed in a forced-air drying oven for a one-pot solvothermal reaction at 80 °C for 1 h. After the reaction is completed, the reactor is allowed to cool naturally. The cooled material is washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain Fe(OH) loaded on the IP current collector. x -Pd@GA nanoarray material (IP / Fe(OH)) x -Pd@GA).

[0073] The material morphology of the obtained product was characterized using SEM. Figure 3 As can be seen from the figure, there is a uniformly distributed nanosheet structure on the IP current collector.

[0074] Example 4: CuM / Cu(OH)2-Ir@ATA Nanoarray Material The preparation method of the CuM / Cu(OH)2-Ir@ATA nanoarray material includes the following steps: (1) Dissolve 1.449 g (3.00 mmol) of potassium hexachloroiridium(IV) (K2IrCl6) in 20 mL of a prepared 2-aminoterephthalic acid (ATA)-ethylene glycol solution (volume ratio 1:10) and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm copper meshes (CuM) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 120 °C for 5 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain Cu(OH)2-Ir@ATA nanoarray material (CuM / Cu(OH)2-Ir@ATA) loaded on CuM current collector.

[0075] The material morphology of the obtained product was characterized using SEM. Figure 4 As can be seen from the figure, there is a uniformly distributed nanosheet structure on the CuM current collector.

[0076] Example 5 CuM / Cu(OH)2-Ir@ZA nanoarray material Same as Example 4, except that 2-aminoterephthalic acid (ATA) is replaced with an equal volume of zoledronic acid (ZA), and the preparation method of the CuM / Cu(OH)2-Ir@ZA nanoarray material includes the following steps: (1) Dissolve 1.449 g (3.00 mmol) of potassium hexachloroiridium(IV) (K2IrCl6) in 20 mL of prepared zoledronic acid (ZA)-ethylene glycol solution (volume ratio 1:10) and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm copper meshes (CuM) were washed and immersed in the mixed solution obtained in step (1). They were then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a drying oven for a one-pot solvothermal reaction at 120 °C for 5 h. After the reaction was completed, the material was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain Cu(OH)2-Ir@ZA nanoarray material (CuM / Cu(OH)2-Ir@ZA) loaded on CuM current collector.

[0077] The material morphology of the obtained product was characterized using SEM. Figure 5 As can be seen from the figure, there is a uniformly distributed nanosheet structure on the CuM current collector.

[0078] Example 6 CuM / Cu(OH)2-Ir@GA nanoarray material Same as Example 4, except that 2-aminoterephthalic acid (ATA) is replaced with an equal volume of gallic acid (GA), and the preparation method of the CuM / Cu(OH)2-Ir@GA nanoarray material includes the following steps: (1) Dissolve 1.449 g (3.00 mmol) of potassium hexachloroiridium(IV) (K2IrCl6) in 20 mL of prepared gallic acid (GA)-ethylene glycol solution (volume ratio 1:10) and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm copper meshes (CuM) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 120 °C for 5 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain Cu(OH)2-Ir@GA nanoarray material (CuM / Cu(OH)2-Ir@GA) loaded on CuM current collector.

[0079] The material morphology of the obtained product was characterized using SEM. Figure 6 As can be seen from the figure, there is a uniformly distributed nanosheet structure on the CuM current collector.

[0080] Example 7 NIP / NiFe-OH-Rh@IPA Nanoarray Material The preparation method of the NIP / NiFe-OH-Rh@IPA nanoarray material includes the following steps: (1) Dissolve 0.326 g (1.00 mmol) of rhodium nitrate (Rh(NO3)3) in 20 mL of prepared isophthalic acid (IPA)-water solution (volume ratio 1:5) and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm nickel-iron alloy plates (NIP) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 160 °C for 10 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain NiFe-OH-Rh@IPA nanoarray material (NIP / NiFe-OH-Rh@IPA) loaded on the NIP current collector.

[0081] The material morphology of the obtained product was characterized using SEM. Figure 7 As can be seen from the figure, the nanosheet-like structure is uniformly distributed on the NIP current collector.

[0082] Example 8: NIP / NiFe-OH-Rh@ATMP Nanoarray Material Same as Example 7, except that isophthalic acid (IPA) is replaced with an equal volume of aminotrimethylenephosphonic acid (ATMP). The preparation method of the NIP / NiFe-OH-Rh@ATMP nanoarray material includes the following steps: (1) Dissolve 0.326 g (1.00 mmol) of rhodium nitrate (Rh(NO3)3) in 20 mL of prepared aminotrimethylenephosphonic acid (ATMP)-water solution (volume ratio 1:5), and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm nickel-iron alloy plates (NIP) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 160 °C for 10 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain NiFe-OH-Rh@ATMP nanoarray material (NIP / NiFe-OH-Rh@ATMP) loaded on the NIP current collector.

[0083] The material morphology of the obtained product was characterized using SEM. Figure 8 As can be seen from the figure, the nanosheet-like structure is uniformly distributed on the NIP current collector.

[0084] Example 9: NIP / NiFe-OH-Rh@EGCG Nanoarray Material Same as Example 7, except that isophthalic acid (IPA) is replaced with an equal volume of epigallocatechin gallate (EGCG), and the preparation method of the NIP / NiFe-OH-Rh@EGCG nanoarray material includes the following steps: (1) Dissolve 0.326 g (1.00 mmol) of rhodium nitrate (Rh(NO3)3) in 20 mL of prepared epigallocatechin gallate (EGCG)-water solution (volume ratio 1:5), and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm nickel-iron alloy plates (NIP) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 160 °C for 10 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain NiFe-OH-Rh@EGCG nanoarray material (NIP / NiFe-OH-Rh@EGCG) loaded on the NIP current collector.

[0085] The obtained product was characterized by SEM. Figure 9 As can be seen from the figure, the nanosheet-like structure is uniformly distributed on the NIP current collector.

[0086] Example 10 NCP / NiCo-OH-Pt@TMA Nanoarray Material The preparation method of the NCP / NiCo-OH-Pt@TMA nanoarray material includes the following steps: (1) Dissolve 0.049 g (0.10 mmol) of potassium chloroplatinate (K2PtCl6) in 20 mL of prepared trimesic acid (TMA)-ethanol solution (volume ratio 1:1) and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm nickel-cobalt alloy plates (NCP) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 40 °C for 40 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain NiCo-OH-Pt@TMA nanoarray material (NCP / NiCo-OH-Pt@TMA) loaded on the NCP current collector.

[0087] The material morphology of the obtained product was characterized using SEM. Figure 10 As can be seen from the figure, there are uniformly distributed nanosheet structures on the NCP current collector.

[0088] Example 11 NCP / NiCo-OH-Pt@ATMP Nanoarray Material Same as Example 10, except that pyromellitic acid (TMA) is replaced with an equal volume of aminotrimethylenephosphonic acid (ATMP). The preparation method of the NCP / NiCo-OH-Pt@ATMP nanoarray material includes the following steps: (1) Dissolve 0.049 g (0.10 mmol) of potassium chloroplatinate (K2PtCl6) in 20 mL of prepared aminotrimethylenephosphonic acid (ATMP)-ethanol solution (volume ratio 1:1), and stir thoroughly on a stirrer for 0.5 h (stirrer speed 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm nickel-cobalt alloy plates (NCP) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 40 °C for 40 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain NiCo-OH-Pt@ATMP nanoarray material (NCP / NiCo-OH-Pt@ATMP) loaded on the NCP current collector.

[0089] The material morphology of the obtained product was characterized using SEM. Figure 11 As can be seen from the figure, there are uniformly distributed nanosheet structures on the NCP current collector.

[0090] Comparative Example 1: IP / Fe(OH) x -Pd nanoarray materials Same as Example 1, except that 4,4'-biphenyl dicarboxylic acid (BPDC) was not added, and the IP / Fe(OH) x The preparation method of Pd nanoarray materials includes the following steps: (1) Dissolve 0.440 g (2.0 mmol) of palladium acetate (Pd(CH3CO2)2) in 20 mL of N,N-dimethylformamide solution and stir thoroughly on a stirrer for 0.5 h (stirrer speed is 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm iron plates (IP) that have been washed clean are immersed in the mixed solution obtained in step (1) and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor is placed in a forced-air drying oven for a one-pot solvothermal reaction at 80 °C for 1 h. After the reaction is completed, the reactor is allowed to cool naturally. The cooled material is washed three times with ethanol and dried in a forced-air drying oven at 60 °C for 12 h to obtain the IP / Fe(OH) loaded on the IP current collector. x -Pd nanoarray materials (IP / Fe(OH)) x -Pd).

[0091] Comparative Example 2: CuM / Cu(OH)2-Ir nanoarray materials Same as Example 4, except that 2-aminoterephthalic acid (ATA) was not added. The preparation method of the CuM / Cu(OH)2-Ir nanoarray material includes the following steps: (1) Dissolve 1.449 g (3.00 mmol) of potassium hexachloroiridium(IV) (K2IrCl6) in 20 mL of ethylene glycol solution and stir thoroughly on a stirrer for 0.5 h (stirrer speed is 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm copper meshes (CuM) were washed and immersed in the mixed solution obtained in step (1). They were then transferred to a high-pressure reactor with a polytetrafluoroethylene liner, sealed, and placed in a drying oven for a one-pot solvothermal reaction at 120 °C for 5 h. After the reaction was completed, the material was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain Cu(OH)2-Ir nanoarray material (CuM / Cu(OH)2-Ir) loaded on CuM current collector.

[0092] Comparative Example 3: NIP / NiFe-OH-Rh Nanoarray Materials Same as Example 7, except that isophthalic acid (IPA) was not added. The preparation method of the NIP / NiFe-OH-Rh nanoarray material includes the following steps: (1) Dissolve 0.326 g (1.00 mmol) of rhodium nitrate (Rh(NO3)3) in 20 mL of aqueous solution and stir thoroughly on a stirrer for 0.5 h (stirrer speed is 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm nickel-iron alloy plates (NIP) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 160 °C for 10 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain NiFe-OH-Rh nanoarray material (NIP / NiFe-OH-Rh) loaded on the NIP current collector.

[0093] Comparative Example 4: NCP / NiCo-OH-Pt Nanoarray Materials Same as Example 10, except that pyromellitic acid (TMA) was not added. The preparation method of the NCP / NiCo-OH-Pt nanoarray material includes the following steps: (1) Dissolve 0.049 g (0.10 mmol) of potassium chloroplatinate (K2PtCl6) in 20 mL of ethanol solution and stir thoroughly on a stirrer for 0.5 h (stirrer speed is 500 rpm) to form a homogeneous mixed solution; (2) Two 1×3 cm nickel-cobalt alloy plates (NCP) were washed and immersed in the mixed solution obtained in step (1), and transferred to a high-pressure reactor with a polytetrafluoroethylene liner. After sealing, the reactor was placed in a drying oven for a one-pot solvothermal reaction at 40 °C for 40 h. After the reaction was completed, the reactor was allowed to cool naturally. The cooled material was washed three times with ethanol and dried in a drying oven at 60 °C for 12 h to obtain NCP / NiCo-OH-Pt nanoarray material (NCP / NiCo-OH-Pt) loaded on the NCP current collector.

[0094] Application Example 1: Performance Testing of Electrocatalytic Seawater Splitting for Hydrogen Evolution (SWHER) Electrochemical testing was conducted using a computer-controlled electrochemical workstation (Autolab, PGSTAT302N) with a standard three-electrode system. The performance indicators for evaluating electrocatalytic materials included the voltage (E) required to achieve the same current density. The stability indicators for evaluating electrocatalytic materials included resistance to chlorine corrosion and resistance to scaling.

[0095] The electrocatalytic performance of the samples was studied in a three-electrode system using an electrode prepared in the examples or comparative examples as the working electrode (1×1 cm), a carbon rod as the counter electrode, and an Hg / HgO electrode (immersed in 1 M KOH solution) as the reference electrode. The potential value E(Hg / HgO) was converted to E(RHE) according to the formula E(RHE) = E(Hg / HgO) + 0.0977 + 0.05916 × pH.

[0096] Before recording the electrocatalytic activity of the catalyst, the catalyst was activated by CV (-1.42 V to -0.92 V vs. Hg / HgO) scanning in a simulated seawater electrolyte (1 M KOH + 0.5 M NaCl, pH = 13.6) under stirring. After the CV scanning results stabilized, the LSV curve (-1.72 V to -0.92 V vs. Hg / HgO) was measured, and the LSV curve was compensated for with 95% iR. Furthermore, the chlorine corrosion resistance and anti-scaling performance of the material were evaluated using chronopotentiometrics (CP). The specific test procedure for chlorine corrosion resistance was as follows: the catalyst was activated by CV (-1.42 V to -0.92 V vs. Hg / HgO) scanning in a simulated seawater electrolyte (1 M KOH + 0.5 M NaCl, pH = 13.6) under stirring. After the CV scanning results stabilized, the catalyst was activated by CV scanning at a current density of 100 mA cm⁻¹. -2CP tests were conducted, and the voltage change over time was recorded. The specific test procedure for anti-scaling stability was as follows: Under stirring, in an electrolyte containing a high concentration of calcium and magnesium salts (0.3 M MgCl2 + 0.03 M MgSO4 + 0.06 M CaCl2, the concentration is approximately 10 times that of real seawater, where CaCl2 is much higher than that of real seawater),... 2+ The concentration is approximately 10 mM, Mg 2+ The concentration was approximately 53 mM). The catalyst was activated by CV scanning. After the CV scanning results stabilized, the catalyst was activated at a current density of 300 mA cm⁻¹. -2 A CP test was performed, and the voltage change over time was recorded.

[0097] This application example relates to Example 1 (IP / Fe(OH)). x -Pd@BPDC), Example 2 (IP / Fe(OH) x -Pd@ZA), Example 3 (IP / Fe(OH) x -Pd@GA), Comparative Example 1 (IP / Fe(OH)) x The SWHER activity and stability of Pd and commercial platinum-carbon electrodes (Pt / C) were tested.

[0098] Depend on Figure 12 It is evident that for the activity of SWHER, IP / Fe(OH) x -Pd@BPDC, IP / Fe(OH) x -Pd@ZA、IP / Fe(OH) x -Pd@GA achieves the same current density of 100 mA·cm -2 Voltage (E) 100 The values ​​were -0.010 V, -0.036 V, and -0.061 V, respectively, and were related to IP / Fe(OH). x The -Pd (-0.105 V) is significantly smaller than that of Pt / C (-0.151 V), indicating that the nanoarray material prepared in the embodiments of the present invention has better SWHER activity.

[0099] Depend on Figure 13 As can be seen, regarding resistance to chlorine corrosion, Example 1 (IP / Fe(OH)) demonstrates superior stability. x -Pd@BPDC) at 100 mA cm -2 It can operate stably for more than 300 hours at a given current density. Example 2 (IP / Fe(OH)) x -Pd@ZA) can operate stably for 100 hours. Example 3 (IP / Fe(OH)) x -Pd@GA) can operate stably for 80 hours, while Comparative Example 1 (IP / Fe(OH)) xThe -Pd electrode only operated stably for 30 hours, and the platinum-carbon electrode (Pt / C) only for 20 hours. These results indicate that, compared to the unmodified Comparative Example 1 (IP / Fe(OH)2), the latter showed significantly better performance. x -Pd) and commercial platinum-carbon electrodes, Example 1 (IP / Fe(OH) x -Pd@BPDC), Example 2 (IP / Fe(OH) x -Pd@ZA), Example 3 (IP / Fe(OH) x -Pd@GA) exhibits better resistance to chlorine corrosion; among them, Example 1 using BPDC modification (IP / Fe(OH)) x -Pd@BPDC has the best resistance to chlorine corrosion.

[0100] Depend on Figure 14 As can be seen, regarding anti-scaling stability, Example 1 (IP / Fe(OH)) x -Pd@BPDC) at 300 mA cm -2 It can remain stable for more than 500 minutes at a current density. Example 2 (IP / Fe(OH)) x -Pd@ZA) can be stably maintained for 160 min, Example 3 (IP / Fe(OH) x -Pd@GA) could maintain a stable state for 120 min, while Comparative Example 1 (IP / Fe(OH)) x The -Pd electrode only maintained stability for 50 min, and the platinum-carbon electrode (Pt / C) only maintained stability for 30 min. These results indicate that, compared to the unmodified Comparative Example 1 (IP / Fe(OH)2), the stability was significantly lower. x -Pd) and commercial platinum-carbon electrodes, Example 1 (IP / Fe(OH) x -Pd@BPDC), Example 2 (IP / Fe(OH) x -Pd@ZA), Example 3 (IP / Fe(OH) x -Pd@GA) exhibits better anti-scaling ability; among them, Example 1 using BPDC modification (IP / Fe(OH)) x -Pd@BPDC has the best anti-scaling effect.

[0101] Application Example 2: Performance Testing of Electrocatalytic Seawater Splitting for Hydrogen Evolution (SWHER) This application example tested the SWHER activity and stability of Example 4 (CuM / Cu(OH)2-Ir@ATA), Example 5 (CuM / Cu(OH)2-Ir@ZA), Example 6 (CuM / Cu(OH)2-Ir@GA), and Comparative Example 2 (CuM / Cu(OH)2-Ir), with specific tests referring to Application Example 1.

[0102] Depend on Figure 15 It is evident that, for the activity of SWHER, CuM / Cu(OH)2-Ir@ATA, CuM / Cu(OH)2-Ir@ZA, and CuM / Cu(OH)2-Ir@GA achieve the same current density of 100 mA·cm. -2 Voltage (E) 100 The values ​​are -0.018 V, -0.054 V, and -0.079 V, respectively, which are significantly smaller than CuM / Cu(OH)2-Ir (-0.129 V), indicating that the nanoarray material prepared in the embodiments of the present invention has better SWHER activity.

[0103] Depend on Figure 16 As can be seen, regarding resistance to chlorine corrosion, Example 4 (CuM / Cu(OH)2-Ir@ATA) showed good resistance at 100 mA cm⁻¹. -2 Under the specified current density, all samples could operate stably for over 200 hours. Example 5 (CuM / Cu(OH)2-Ir@ZA) operated stably for 100 hours, Example 6 (CuM / Cu(OH)2-Ir@GA) operated stably for 90 hours, while Comparative Example 2 (CuM / Cu(OH)2-Ir) only operated for 60 hours. These results indicate that, compared to the unmodified Comparative Example 2 (CuM / Cu(OH)2-Ir), Examples 4 (CuM / Cu(OH)2-Ir@ATA), 5 (CuM / Cu(OH)2-Ir@ZA), and 6 (CuM / Cu(OH)2-Ir@GA) exhibited better resistance to chlorine corrosion; among them, Example 4 (CuM / Cu(OH)2-Ir@ATA), modified with ATA, showed the best resistance to chlorine corrosion.

[0104] Depend on Figure 17 As can be seen, regarding anti-scaling stability, Example 4 (CuM / Cu(OH)2-Ir@ATA) showed good performance at 300 mA cm⁻¹. -2At the specified current density, the samples maintained a stable state for over 400 min. Example 5 (CuM / Cu(OH)2-Ir@ZA) maintained a stable state for 80 min, Example 6 (CuM / Cu(OH)2-Ir@GA) maintained a stable state for 60 min, while Comparative Example 2 (CuM / Cu(OH)2-Ir) only maintained a stable state for 30 min. These results indicate that, compared to the unmodified Comparative Example 2 (CuM / Cu(OH)2-Ir), Examples 4 (CuM / Cu(OH)2-Ir@ATA), 5 (CuM / Cu(OH)2-Ir@ZA), and 6 (CuM / Cu(OH)2-Ir@GA) exhibit better anti-scaling capabilities; among them, Example 4 (CuM / Cu(OH)2-Ir@ATA), modified with ATA, showed the best anti-scaling effect.

[0105] Application Example 3: Performance Testing of Electrocatalytic Seawater Splitting for Hydrogen Evolution (SWHER) This application example tested the SWHER activity and stability of Example 7 (NIP / NiFe-OH-Rh@IPA), Example 8 (NIP / NiFe-OH-Rh@ATMP), Example 9 (NIP / NiFe-OH-Rh@EGCG), and Comparative Example 3 (NIP / NiFe-OH-Rh), with specific tests conducted according to Application Example 1.

[0106] Depend on Figure 18 It is evident that for SWHER activity, NIP / NiFe-OH-Rh@IPA, NIP / NiFe-OH-Rh@ATMP, and NIP / NiFe-OH-Rh@EGCG achieve the same current density of 100 mA·cm⁻¹. -2 Voltage (E) 100 The values ​​of -0.028 V, -0.068 V, and -0.089 V are respectively, which are significantly smaller than those of NIP / NiFe-OH-Rh (-0.132 V), indicating that the nanoarray material prepared in the embodiments of the present invention has better SWHER activity.

[0107] Depend on Figure 19 As can be seen, regarding resistance to chlorine corrosion, Example 7 (NIP / NiFe-OH-Rh@IPA) exhibits good resistance at 100 mA cm⁻¹. -2Under the specified current density, all samples could operate stably for over 300 hours. Example 8 (NIP / NiFe-OH-Rh@ATMP) operated stably for 120 hours, Example 9 (NIP / NiFe-OH-Rh@EGCG) operated stably for 90 hours, while Comparative Example 3 (NIP / NiFe-OH-Rh) only operated for 60 hours. These results indicate that, compared to the unmodified Comparative Example 3 (NIP / NiFe-OH-Rh), Examples 7 (NIP / NiFe-OH-Rh@IPA), 8 (NIP / NiFe-OH-Rh@ATMP), and 9 (NIP / NiFe-OH-Rh@EGCG) exhibit better resistance to chlorine corrosion; among them, Example 7 (NIP / NiFe-OH-Rh@IPA), modified with IPA, showed the best resistance to chlorine corrosion.

[0108] Depend on Figure 20 As can be seen, regarding anti-fouling stability, Example 7 (NIP / NiFe-OH-Rh@IPA) showed good performance at 300 mA cm⁻¹. -2 At the specified current density, the samples maintained stable stability for over 450 min. Example 8 (NIP / NiFe-OH-Rh@ATMP) maintained stability for 130 min, Example 9 (NIP / NiFe-OH-Rh@EGCG) maintained stability for 90 min, while Comparative Example 3 (NIP / NiFe-OH-Rh) only maintained stability for 55 min. These results indicate that, compared to the unmodified Comparative Example 3 (NIP / NiFe-OH-Rh), Examples 7 (NIP / NiFe-OH-Rh@IPA), 8 (NIP / NiFe-OH-Rh@ATMP), and 9 (NIP / NiFe-OH-Rh@EGCG) exhibit better anti-scaling capabilities; among them, Example 7 (NIP / NiFe-OH-Rh@IPA), modified with IPA, showed the best anti-scaling effect.

[0109] Application Example 4: Performance Testing of Electrocatalytic Seawater Splitting for Hydrogen Evolution (SWHER) This application example tested the SWHER activity and stability of Example 10 (NCP / NiCo-OH-Pt@TMA), Example 11 (NCP / NiCo-OH-Pt@ATMP), and Comparative Example 4 (NCP / NiCo-OH-Pt), with specific tests conducted according to Application Example 1.

[0110] Depend on Figure 21 It is evident that for the activity of SWHER, NCP / NiCo-OH-Pt@TMA and NCP / NiCo-OH-Pt@ATMP achieve the same current density of 100 mA·cm⁻¹. -2 Voltage (E) 100The values ​​are -0.082 V and -0.116 V, respectively, which are significantly smaller than those of NCP / NiCo-OH-Pt (-0.213 V), indicating that the nanoarray material prepared in the embodiments of the present invention has better SWHER activity.

[0111] Depend on Figure 22 As can be seen, regarding resistance to chlorine corrosion, Example 10 (NCP / NiCo-OH-Pt@TMA) exhibits good resistance at 100 mAcm⁻¹. -2 At the specified current density, both examples can operate stably for over 320 hours. Example 11 (NCP / NiCo-OH-Pt@ATMP) can operate stably for 110 hours, while Comparative Example 4 (NCP / NiCo-OH-Pt) can only operate for 30 hours. These results indicate that, compared to the unmodified Comparative Example 4 (NCP / NiCo-OH-Pt), Examples 10 (NCP / NiCo-OH-Pt@TMA) and 11 (NCP / NiCo-OH-Pt@ATMP) have better resistance to chlorine corrosion; among them, Example 10 (NCP / NiCo-OH-Pt@TMA), modified with TMA, exhibits the best resistance to chlorine corrosion.

[0112] Depend on Figure 23 As can be seen, regarding anti-fouling stability, Example 10 (NCP / NiCo-OH-Pt@TMA) showed good performance at 300 mA cm⁻¹. -2 At the specified current density, the samples maintained stable stability for over 400 min. Example 11 (NCP / NiCo-OH-Pt@ATMP) maintained stable stability for 100 min, while Comparative Example 4 (NCP / NiCo-OH-Pt) only maintained stable stability for 30 min. These results indicate that, compared to the unmodified Comparative Example 4 (NCP / NiCo-OH-Pt), Examples 10 (NCP / NiCo-OH-Pt@TMA) and 11 (NCP / NiCo-OH-Pt@ATMP) exhibit better anti-scaling capabilities; among them, Example 10 (NCP / NiCo-OH-Pt@TMA), modified with TMA, showed the best anti-scaling effect.

[0113] In summary, compared with unmodified materials and commercial platinum-carbon electrodes, the materials prepared in this invention exhibit significant advantages in catalytic activity, corrosion resistance, and anti-fouling stability. Among them, the material modified with organic polycarboxylic acid compounds shows the best performance: achieving 100 mA·cm⁻¹ in the hydrogen evolution reaction of seawater electrolysis. -2 It requires the lowest potential (as low as -0.010 V) and can operate stably for more than 200 hours in simulated seawater electrolytes; it can still operate stably for more than 400 minutes in electrolytes with a high risk of scaling, where the calcium and magnesium ion concentration is about 10 times that of real seawater.

[0114] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a surface-modified transition metal hydroxide-supported noble metal nanoarray material, characterized in that, Includes the following steps: The transition metal-based current collector was immersed in a solution containing noble metal salts and multifunctional organic molecular modifiers to carry out a solvothermal reaction. After post-treatment, the surface-modified transition metal hydroxide-supported noble metal nanoarray material was obtained. The multifunctional organic molecule modifier is selected from at least one of organic polycarboxylic acid compounds, organic polyphosphate compounds, and polyphenolic compounds.

2. The preparation method according to claim 1, characterized in that, The multifunctional organic molecule modifier is an organic polycarboxylic acid compound.

3. The preparation method according to claim 2, characterized in that, The organic polycarboxylic acid compound is selected from at least one of 4,4'-biphenyldicarboxylic acid, 2-aminoterephthalic acid, isophthalic acid, and pyromellitic acid.

4. The preparation method according to claim 1, characterized in that, The noble metal in the noble metal salt is selected from at least one of Pt, Ru, Pd, Ir, Os, Rh, Au, and Ag.

5. The preparation method according to claim 1, characterized in that, The transition metal in the transition metal-based current collector is selected from at least one of Fe, Co, Ni, Cu, Ti, and Mo.

6. The preparation method according to claim 1, characterized in that, The concentration of the noble metal salt in the solution containing the noble metal salt and the multifunctional organic molecule modifier is 2.5~250 mmol / L.

7. The preparation method according to claim 1, characterized in that, The solvent in the solution containing the noble metal salt and the multifunctional organic molecule modifier is selected from at least one of water, methanol, ethanol, ethylene glycol, isopropanol, acetone, N,N-dimethylformamide, and dimethyl sulfoxide.

8. The preparation method according to claim 7, characterized in that, The volume ratio of the multifunctional organic molecule modifier to the solvent is 1:(0.5~150).

9. The surface-modified transition metal hydroxide-supported noble metal nanoarray material prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the surface-modified transition metal hydroxide-supported noble metal nanoarray material of claim 9 in the hydrogen evolution reaction of water electrolysis.

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