Black phosphorus modified platinum nanotube array and preparation method and application thereof

Abstract

The present application relates to a kind of black phosphorus modified platinum nanotube array and its preparation method and application, specifically, the method for preparing black phosphorus modified platinum nanotube array by zinc oxide template assisted electrochemical co-deposition is used to improve the performance of water electrolysis hydrogen evolution reaction, especially the performance of alkaline medium hydrogen evolution reaction.The present application uses conductive material as substrate, by constant current template assisted electrodeposition, zinc oxide nanorod array loaded on conductive substrate is obtained, then black phosphorus modified platinum nanorod array is prepared by constant current electrochemical co-deposition, finally, after removing zinc oxide template by corrosive aqueous solution, black phosphorus modified platinum nanotube array is obtained.As hydrogen evolution catalyst, it can significantly reduce the cathode overpotential of water electrolysis, while reducing the loading amount of noble metal, with high energy conversion efficiency and economic benefit.The black phosphorus modified platinum nanotube array prepared by the method has excellent electrocatalytic performance, and the catalyst preparation process has good reproducibility and can be scaled up, with commercial application potential.

Description

Technical Field

[0001] This invention relates to the field of electrocatalytic hydrogen evolution technology, specifically to a method for preparing a black phosphorus-modified platinum nanotube array and its application in the electrolysis of water for hydrogen evolution, particularly in the efficient electrolysis of water for hydrogen evolution in alkaline aqueous solutions. Background Technology

[0002] Hydrogen production via water electrolysis powered by renewable energy plays a crucial role in hydrogen energy development and energy conversion. The hydrogen evolution reaction (HER) is a vital component of water electrolysis, and researchers have made significant progress in improving HER efficiency over the years through the careful design of highly active platinum (Pt)-based electrocatalysts. Currently, water electrolysis in alkaline media offers advantages over acidic media because it avoids acid mist generation and produces hydrogen with higher purity. Furthermore, the membranes used in alkaline electrolyzers are more economical than those used in acidic media, reducing the cost of commercializing water electrolysis (ACS Materials Letters, 2021, 3, 224-234). However, since there are no hydrogen protons in the alkaline medium, the energy barrier of water dissociation must first be overcome before the hydrogen evolution reaction can continue. Pt atoms have a poor ability to activate water molecules, which results in the kinetics of the hydrogen evolution reaction in alkaline media being 2-3 orders of magnitude slower than in acidic media (Angewandte Chemie International Edition, 2021, 60, 18981-19006). Besides the slow kinetics, Pt-based catalysts also suffer from poor long-term stability in alkaline media, hindering the progress of Pt-based catalysts in alkaline water electrolysis for hydrogen production. According to the kinetic steps of HER, two key factors affect the catalytic performance of HER in alkaline media: (1) the water dissociation energy barrier; and (2) the adsorption strength of hydrogen intermediates (Nature Energy, 2020, 5, 891-899). By adjusting and optimizing these two key factors, high-performance and low-cost Pt-based HER electrocatalysts in alkaline media can be prepared. Studies have shown that doping or modifying Pt-based catalysts with non-metallic elements (such as N, P, and S) can lower the energy barrier for water dissociation and optimize the adsorption strength of hydrogen intermediates. Further combining this with morphology control strategies (such as nanowires, nanosheets, and nanotubes) can increase the number of active sites, thereby enhancing the HER activity and stability of Pt-based catalysts in alkaline media. Black phosphorus not only possesses a honeycomb structure but also has a highly exposed active surface and high carrier mobility, allowing its surface lone pair electrons to be fully exposed. These advantages make black phosphorus a promising candidate for electrocatalytic HER. It has been confirmed that black phosphorus, as a phosphorus source, has a unique activation effect on Pt atoms. The surface electron cloud density of Pt atoms activated by black phosphorus changes, thereby improving the hydrogen evolution performance in alkaline media (Angewandte Chemie International Edition, 2019, 58, 19060-19066). This strategy of combining black phosphorus with platinum-based catalysts can enhance the water dissociation ability of Pt atoms, improving the catalyst's hydrogen evolution catalytic stability and water electrolysis efficiency. Summary of the Invention

[0003] The purpose of this invention is to provide a black phosphorus-modified platinum nanotube array and its preparation method, and to use it as a cathode hydrogen evolution catalyst for water electrolysis, especially for hydrogen evolution in alkaline media. The synthesis process is simple, and the prepared black phosphorus-modified platinum nanotube array catalyst exhibits excellent hydrogen evolution performance in aqueous solutions with pH values ​​ranging from 2 to 13. The black phosphorus-modified platinum nanotube array effectively reduces the overpotential of the cathode hydrogen evolution reaction, particularly significantly improving hydrogen evolution performance in alkaline media, while also reducing the loading of the precious metal platinum, thus significantly improving energy conversion efficiency.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: This invention provides a method for preparing black phosphorus-modified platinum nanotube arrays by zinc oxide template-assisted electrochemical co-deposition, the specific steps of which are as follows: (1) The conductive substrate is placed vertically in a mixed aqueous solution of zinc nitrate and ammonium nitrate A. Under heating conditions, a conductive electrode is used as the counter electrode in a two-port electrolytic cell, and a zinc oxide nanorod array is obtained by constant current electrodeposition.

[0005] (2) The zinc oxide nanorod array obtained in step (1) is placed vertically in a mixed aqueous solution B of chloroplatinic acid and black phosphorus. Under heating conditions, a nanorod array loaded with platinum and phosphorus is obtained by constant current electrochemical co-deposition in a two-port electrolytic cell using a conductive electrode as the counter electrode.

[0006] (3) The nanorod array obtained in step (2) is placed vertically in a corrosive aqueous solution to remove the zinc oxide template, resulting in a three-dimensional self-supporting platinum nanotube array modified with black phosphorus loaded on a conductive substrate.

[0007] Furthermore, the conductive electrode used in step (1) can be a carbon rod, platinum sheet, or platinum wire; the conductive substrate is a conductive material such as carbon cloth, copper foam, nickel foam, or ultrathin metal sheet, preferably carbon cloth. For example, the carbon cloth is first cut into pieces with an area ranging from 4 to 20 cm². 2 Then, soak in acetone for 6-12 hours to remove surface impurities, then ultrasonically clean with a mixed solution of concentrated nitric acid and concentrated sulfuric acid at 30-100℃ for 5-60 minutes, and finally clean with ultrapure water and dry.

[0008] Further, in step (1), the concentration of zinc nitrate in the mixed aqueous solution A ranges from 0.01 M to 0.1 M, preferably 0.01 M, and the concentration of ammonium nitrate ranges from 0.01 M to 0.1 M, preferably 0.05 M. The electrodeposition temperature is 70-100 °C, preferably 70 °C, and the current density is 0.5-10 mA cm⁻¹. -2 Preferably 1 mA cm -2The electrodeposition time is 60-120 min, preferably 90 min.

[0009] Furthermore, in step (2), the concentration of chloroplatinic acid in the mixed aqueous solution B ranges from 0.1 to 5 mM, the concentration of black phosphorus ranges from 0.1 to 5 mM, the electrodeposition temperature is 30-100℃, preferably 35℃, and the current density is 0.1-5 mA cm⁻¹. -2 Preferred 1mA cm -2 The electrodeposition time is 15-90 min, preferably 60 min.

[0010] Furthermore, the corrosive aqueous solution in step (3) is an acidic aqueous solution with a pH less than 3 or an alkaline aqueous solution with a pH greater than 12, preferably an alkaline aqueous solution with a pH greater than 12, and the soaking time is 3-12 h, preferably 4 h.

[0011] This invention provides a method for preparing black phosphorus-modified platinum nanotube arrays. This invention also provides the application of black phosphorus-modified platinum nanotube arrays in promoting hydrogen evolution in water electrolysis in aqueous solutions with pH = 2-13. The black phosphorus-modified platinum nanotube arrays achieve a hydrogen evolution reaction of 150 mA cm⁻¹ in acidic electrolytes. -2 The overpotential required at the required current density is less than 90 mV; reaching 50 mA cm⁻¹ in a neutral electrolyte. -2 The overpotential required at the required current density is less than 100 mV; in alkaline electrolytes, it reaches 300 mA cm⁻¹. -2 The required overpotential for the current density is less than 280 mV.

[0012] The beneficial effects of this invention are as follows: This invention, through black phosphorus-modified platinum nanotube array catalyst, effectively reduces the cathode hydrogen evolution overpotential in water electrolysis reactions at pH 2-13, especially in alkaline aqueous solutions. Simultaneously, it reduces the amount of precious metals required, resulting in high energy conversion efficiency and economic benefits. The synthesis process of this invention is simple and can be scaled up. The prepared catalyst exhibits excellent electrocatalytic hydrogen evolution performance, requiring a relatively small cathode electrode potential to achieve high current densities, and demonstrating high hydrogen evolution efficiency in water electrolysis, indicating broad application prospects. Attached Figure Description

[0013] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0014] Figure 1The X-ray photoelectron spectra of Embodiment 1, Comparative Example 1, and Comparative Example 2 of the present invention are shown.

[0015] Figure 2 This is a transmission electron microscope (TEM) image of the nanotube catalyst prepared in Example 1 of the present invention.

[0016] Figure 3 The polarization curves of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 of this invention in 0.5 M sulfuric acid aqueous solution are shown.

[0017] Figure 4 The polarization curves of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 of this invention in 1.0 M buffer aqueous solution are shown.

[0018] Figure 5 The polarization curves of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 of this invention in 1.0 M potassium hydroxide aqueous solution are shown. Detailed Implementation

[0019] The present invention will be further described below with reference to specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above-described invention.

[0020] Example 1 (BP-Pt(1:1)) The preparation method of the black phosphorus modified platinum (BP-Pt(1:1)) nanotube array in this embodiment is as follows: (1) The area range is 4 to 20 cm 2 The treated carbon cloth substrate was placed vertically in a mixed aqueous solution of 0.01 M zinc nitrate and 0.05 M ammonium nitrate, and electrolyzed at 70 °C in a dual-port electrolytic cell using a carbon rod as the counter electrode and a 1 mA cm⁻¹ electrode. -2 A zinc oxide nanorod array was obtained by constant current electrodeposition for 90 min.

[0021] (2) The obtained zinc oxide nanorod array was vertically placed in a mixed aqueous solution of 0.7 mM chloroplatinic acid and 0.7 mM black phosphorus. At 35 °C, using carbon rods as the counter electrode, a 0.5 mA cm⁻¹ electrolytic cell was used. -2 A platinum and phosphorus-loaded nanorod array was obtained by constant current electrochemical co-deposition for 60 min.

[0022] (3) The nanorod array obtained in step (2) was placed vertically in an alkaline aqueous solution with a pH greater than 12 to remove the zinc oxide template, and a black phosphorus modified platinum nanotube array was obtained (in the name BP-Pt(1:1) indicates that the molar concentration ratio of black phosphorus and chloroplatinic acid in the electrolyte is 1:1, and the naming method of the following examples is the same as that of Example 1).

[0023] Table 1. ICP detection results of the catalyst prepared in Example 1 catalyst BP-Pt (1:1) (Pt) BP-Pt (1:1) (P) Sediment mass (ug) 150 8 Table 1 shows the mass of platinum and phosphorus elements loaded on the conductive carbon cloth substrate in Example 1.

[0024] Example 2 (BP-Pt(1:3)) The preparation method of the black phosphorus modified platinum (BP-Pt(1:3)) nanotube array in this embodiment is as follows: (1) The area range is 4 to 20 cm 2 The treated carbon cloth was placed vertically in a mixed aqueous solution of 0.01 M zinc nitrate and 0.05 M ammonium nitrate, and electrolyzed at 70 °C in a dual-port electrolytic cell using a carbon rod as the counter electrode and a 1 mA cm⁻¹ electrode. -2 A zinc oxide nanorod array was obtained by constant current electrodeposition for 90 min.

[0025] (2) The obtained zinc oxide nanorod array was vertically placed in a mixed aqueous solution containing 1.0 mM chloroplatinic acid and 0.33 mM black phosphorus, and electrolyzed at 35 °C in a two-port electrolytic cell using carbon rods as the counter electrode and a 0.5 mA cm⁻¹ electrode. -2 A platinum and phosphorus-loaded nanorod array was obtained by constant current electrochemical co-deposition for 60 min.

[0026] (3) The nanorod array obtained in step (2) is placed vertically in an alkaline aqueous solution with a concentration greater than 12 to remove the zinc oxide template, thereby obtaining a black phosphorus modified platinum nanotube array.

[0027] Example 3 (BP-Pt(2:1)) The preparation method of the black phosphorus modified platinum (BP-Pt(2:1)) nanotube array in this embodiment is as follows: (1) The area range is 4 to 20 cm 2 The treated carbon cloth was placed vertically in a mixed aqueous solution of 0.01 M zinc nitrate and 0.05 M ammonium nitrate, and electrolyzed at 70 °C in a dual-port electrolytic cell using a carbon rod as the counter electrode and a 1 mA cm⁻¹ electrode. -2 A zinc oxide nanorod array was obtained by constant current electrodeposition for 90 min.

[0028] (2) The obtained zinc oxide nanorod array was vertically placed in a mixed aqueous solution of 0.5 mM chloroplatinic acid and 1.0 mM black phosphorus, and electrolyzed at 35 °C in a two-port electrolytic cell using carbon rods as the counter electrode and 0.5 mA cm⁻¹. -2 A platinum and phosphorus-loaded nanorod array was obtained by constant current electrochemical co-deposition for 60 min.

[0029] (3) The nanorod array obtained in step (2) is placed vertically in an alkaline aqueous solution with pH greater than 12 to remove the zinc oxide template, and a black phosphorus modified platinum nanotube array is obtained.

[0030] Comparative Example 1 (BP) (1) The area range is 4 to 20 cm 2 The treated carbon cloth was placed vertically in a mixed aqueous solution of 0.01 M zinc nitrate and 0.05 M ammonium nitrate, and electrolyzed at 70 °C in a dual-port electrolytic cell using a carbon rod as the counter electrode and a 1 mA cm⁻¹ electrode. -2 A zinc oxide nanorod array was obtained by constant current electrodeposition for 90 min.

[0031] (2) The obtained zinc oxide nanorod array was vertically placed in a 1.5 mM black phosphorus aqueous solution and electrolyzed at 35 °C in a two-port electrolytic cell using carbon rods as the counter electrode and a 0.5 mA cm⁻¹ polarity. -2 A nanorod array loaded with phosphorus was obtained by constant current electrochemical deposition for 60 min.

[0032] (3) The nanorod array obtained in step (2) is placed vertically in an alkaline aqueous solution with pH greater than 12 to remove the zinc oxide template and obtain a phosphorus-loaded catalyst.

[0033] Comparative Example 2 (Pt) (1) The area range is 4 to 20 cm 2 The treated carbon cloth was placed vertically in a mixed aqueous solution of 0.01 M zinc nitrate and 0.05 M ammonium nitrate, and electrolyzed at 70 °C in a dual-port electrolytic cell using a carbon rod as the counter electrode and a 1 mA cm⁻¹ electrode. -2 A zinc oxide nanorod array was obtained by constant current electrodeposition for 90 min.

[0034] (2) The obtained zinc oxide nanorod array was vertically placed in an aqueous solution of 1.15 mM chloroplatinic acid and electrolyzed at 35 °C in a two-port electrolytic cell using carbon rods as the counter electrode and a current of 0.5 mA cm⁻¹. -2 A nanorod array loaded with platinum was obtained by constant current electrochemical deposition for 60 min.

[0035] (3) The nanorod array obtained in step (2) is placed vertically in an alkaline aqueous solution with pH greater than 12 to remove the zinc oxide template and obtain a platinum nanotube array.

[0036] Comparative Example 3 (BP-Pt(1:1) Nanosheets) (1) The area range is 4 to 20 cm 2The treated carbon cloth was placed vertically in a mixed aqueous solution of 0.01 M zinc nitrate and 0.05 M ammonium nitrate, and electrolyzed at 70 °C in a dual-port electrolytic cell using a carbon rod as the counter electrode and a 1 mA cm⁻¹ electrode. -2 A zinc oxide nanorod array was obtained by constant current electrodeposition for 90 min.

[0037] (2) The obtained zinc oxide nanorod array was vertically placed in a potassium chloride aqueous solution with a concentration range of 0.001–0.01 mM. The mixture was then electrolyzed at 35 °C in a two-port electrolytic cell using carbon rods as the counter electrode and a 0.5 mA cm⁻¹ electrode. -2 Constant current electrochemical reduction for 120 min yielded elemental zinc loaded on carbon cloth.

[0038] (3) The zinc element loaded on the carbon cloth was placed in a weakly acidic (pH 5-7) aqueous solution for 4-6 h to obtain zinc oxide nanosheet array.

[0039] (4) The obtained zinc oxide nanosheet array was vertically placed in a 0.7 mM chloroplatinic acid and 0.7 mM black phosphorus aqueous solution, and electrolyzed at 35 °C in a two-port electrolytic cell using a carbon rod as the counter electrode and a 0.5 mA cm⁻¹ electrode. -2 Constant current electrochemical deposition for 60 min yielded platinum and phosphorus nanosheets loaded on a zinc oxide template.

[0040] (5) The nanosheet array obtained in step (4) is placed vertically in an alkaline aqueous solution with a pH greater than 12 to remove the zinc oxide template, thereby obtaining a black phosphorus modified platinum nanosheet array.

[0041] A three-dimensional self-supporting nanotube catalyst supported on carbon cloth was used as the working electrode, an Ag / AgCl electrode as the reference electrode, and a platinum sheet electrode as the counter electrode. The electrochemical hydrogen evolution performance of the catalyst was evaluated in a three-electrode system. The potential referenced the reversible hydrogen electrode (RHE): E RHE =E Ag / AgCl +0.098 +0.059 × pH. Polarization curves of Examples 1-3 and Comparative Examples 1-3 in electrolytes with pH = 2-13 were tested at a scan rate of 0.05 V / s. Analysis showed that in acidic media, Examples 1-3 achieved a polarization rate of 150 mA cm⁻¹. -2 The required cathode overpotential at current densities is lower than that of Comparative Examples 1 to 3, with Example 1 achieving 150 mA cm⁻¹. -2 The minimum overpotential required at current density is 70 mV, see [reference]. Figure 3 In a neutral medium, Examples 1-3 achieved 50 mA cm⁻¹ -2 The required cathode overpotential at the current density is lower than that of Comparative Examples 1-3, with Example 3 achieving 50 mA cm⁻¹.-2 The minimum overpotential required at current density is 60 mV, see [reference]. Figure 4 In an alkaline medium, Examples 1-3 achieved a flow rate of 300 mA cm⁻¹. -2 The required cathode overpotential at current densities is lower than that of Comparative Examples 1 to 3, with Example 1 achieving 300 mA cm⁻¹. -2 The minimum overpotential required at current density is 190 mV, see [reference]. Figure 5 Test results show that all examples exhibit superior hydrogen evolution catalytic performance compared to comparative examples 1–3 in electrolytes with pH values ​​ranging from 2 to 13. Voltage drop compensation was applied to all electrode potential data.

[0042] Figure 1 These are the X-ray photoelectron spectra of Embodiment 1, Comparative Example 1, and Comparative Example 2 of the present invention. Figure 1 As shown, it can be seen that Comparative Example 1 only has the elemental peak of phosphorus, Comparative Example 2 only has the elemental peak of platinum, while Example 1 shows obvious characteristic peaks of phosphorus and platinum, indicating that the black phosphorus modified platinum nanotube array structure was successfully prepared (Note: the dashed lines mark the impurity peaks generated by residual elements during the black phosphorus preparation process).

[0043] Figure 2 This is a transmission electron microscope (TEM) image of the BP-Pt(1:1) nanotube array prepared in Example 1 of this invention. The image shows that the morphology of Example 1 is a hollow nanotube structure.

[0044] Figure 3 The graphs show the polarization curves of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 of this invention in 0.5 M sulfuric acid aqueous solution. The graphs show that at 150 mA cm⁻¹... -2 At the current density, the overpotential required for Examples 1 to 3 is less than that for Comparative Examples 1 to 3, and the overpotential required for Example 1 is the smallest, indicating that it has the best hydrogen evolution catalytic performance in acidic aqueous solution.

[0045] Figure 4 The graphs show the polarization curves of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 of this invention in a 1.0 M buffer aqueous solution. The graphs show that at 50 mA cm⁻¹... -2 At the current density, the overpotential required for Examples 1 to 3 is less than that for Comparative Examples 1 to 3, and the overpotential required for Example 3 is the smallest, indicating that it has the best hydrogen evolution catalytic performance in neutral aqueous solution.

[0046] Figure 5 The graphs show the polarization curves of the catalysts prepared in Examples 1-3 and Comparative Examples 1-3 of this invention in a 1.0 M potassium hydroxide aqueous solution. The graphs show that at 300 mA cm⁻¹... -2At the current density, the overpotential required for Examples 1 to 3 is less than that for Comparative Examples 1 to 3, and the overpotential required for Example 1 is the smallest, indicating that it has the best hydrogen evolution catalytic performance in alkaline aqueous solution.

[0047] The foregoing has shown and described the basic principles and main features of the present invention, as well as its advantages. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a black phosphorus-modified platinum nanotube array, characterized in that... Includes the following steps: (1) The conductive substrate is placed vertically in a mixed aqueous solution A of zinc nitrate and ammonium nitrate, and under heating conditions, it is subjected to two-port electrolysis. In the tank, using a conductive electrode as the counter electrode, constant current electrodeposition was employed to obtain densely grown zinc oxide nanoparticles on a conductive substrate. Rice bar array; (2) The zinc oxide nanorod array obtained in step (1) is placed vertically in a mixed aqueous solution B containing chloroplatinic acid and black phosphorus. In a dual-electrode cell under heating conditions, using a conductive electrode as the counter electrode, electrochemical co-deposition with constant current is performed to obtain... Black phosphorus-modified platinum nanorod arrays grown on zinc oxide templates; (3) The black phosphorus-modified platinum nanorod array obtained in step (2) was placed vertically in a corrosive aqueous solution to remove zinc oxide. Templates were used to obtain a three-dimensional self-supporting platinum nanotube array modified with black phosphorus loaded on a conductive substrate. In step (1), the concentration range of zinc nitrate in the mixed aqueous solution A is 0.01 M to 0.1 M, the concentration range of ammonium nitrate is 0.01 M to 0.1 M, the constant current electrodeposition temperature is 70 to 100 °C, and the current density is 0.5 to 10 mA cm⁻¹. -2 The constant current electrodeposition time is 60–120 min; In step (2), the concentration range of chloroplatinic acid in the mixed aqueous solution B is 0.1–5 mM, the concentration range of black phosphorus is 0.1–5 mM, the temperature of galvanostatic electrochemical co-deposition is 30–100 °C, and the current density of galvanostatic electrochemical co-deposition is 0.1–5 mA cm⁻¹. -2 The time for constant current electrochemical co-deposition is 15–90 min.

2. The method for preparing black phosphorus-modified platinum nanotube arrays according to claim 1, characterized in that: The steps (1) The conductive substrate is carbon cloth, copper foam, nickel foam, or ultrathin metal sheet, wherein when the conductive substrate is carbon cloth, it is cut into pieces with an area ranging from 4 to 20 cm². 2 The carbon cloth is then soaked in acetone for 6–12 h to remove surface impurities, and then ultrasonically cleaned with a mixture of concentrated nitric acid and concentrated sulfuric acid at 30–100 °C for 5–60 min. After that, it is washed with ultrapure water and then dried. The conductive electrodes used in steps (1) and (2) are carbon rods, platinum sheets or platinum wires.

3. The method for preparing black phosphorus-modified platinum nanotube arrays according to claim 1, characterized in that: The corrosive aqueous solution in step (3) is an acidic aqueous solution with a pH less than 3 or an alkaline aqueous solution with a pH greater than 12, and the soaking time is 3-12 hours.

4. The black phosphorus-modified platinum nanotube array prepared by the preparation method according to any one of claims 1-3.

5. The application of the black phosphorus-modified platinum nanotube array according to claim 4 in the hydrogen evolution reaction of water electrolysis.

6. The application according to claim 5, characterized in that: The electrolyte is an aqueous solution with pH = 2 to 13.

7. The application according to claim 6, characterized in that: Black phosphorus-modified platinum nanotube arrays achieved [results] in acidic electrolytes. up to 150 mA cm -2 The required overpotential at the current density is less than 90 mV, and reaches 50 mAcm in neutral electrolytes. -2 The required overpotential at the current density is less than 100 mV, and reaches 300 mA cm⁻¹ in alkaline electrolytes. -2 The required overpotential for the current density is less than 280 mV.

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