A preparation method of a micro-cone array electrode structure for catalyzing active ejection separation of interface bubbles

Abstract

The application relates to a preparation method of a micro-cone array electrode structure for catalyzing active ejection separation of an interface bubble, and belongs to the technical field of water electrolysis hydrogen production and bubble power control. The electrode bottom plate and the micro-cone structure are printed based on surface projection micro-stereolithography printing technology; and the catalytic performance of water electrolysis hydrogen production is given through chemical deposition. The bubble on the micro-cone array electrode is subjected to the force generated at the interface between the bubble and the micro-cone electrode surface, that is, the upward resultant force of the bubble driving force and the buoyancy, so as to drive the bubble to be ejected upward between the micro-cone electrodes, and then active ejection separation is realized. The structure size of the micro-cone is changed to control the size of the bubble, and the ejection separation of all bubbles is realized, so as to promote ion exchange in the water electrolysis hydrogen production reaction and accelerate the efficient performance of the water electrolysis hydrogen production reaction.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of water electrolysis hydrogen production and bubble power control, and particularly relates to a preparation method of a micro-cone array electrode structure for active ejection separation of catalytic interface bubbles. BACKGROUND

[0002] In the field of electrolytic hydrogen production, improving electrolysis efficiency and realizing large-area industrial application are key goals. Currently, there are many challenges in the process of electrolytic hydrogen production, among which the problem of bubble adhesion on the surface of the electrode catalyst is particularly prominent. When bubbles adhere to the surface of the electrode catalyst, they will hinder the effective contact between the electrode and the electrolyte, increase the electrolysis resistance, reduce the reaction rate, and ultimately greatly reduce the overall electrolysis efficiency.

[0003] To address this problem, existing electrode surface bubble control technologies have emerged, such as asymmetric geometric gradient self-supporting electrodes and nanoparticle structure interface electrodes. These technologies have improved the bubble problem in the process of water electrolysis hydrogen production to some extent and have been widely used in this field. However, they still have obvious limitations. In terms of precise control and transport of hydrogen bubbles, these technologies are difficult to achieve consistent control of bubble size, and the bubble separation efficiency is also unstable, which forms a bottleneck for further improvement of electrolysis efficiency. At the same time, their preparation cost is relatively high, and the processing technology is complex, which is not conducive to large-scale popularization and application.

[0004] In addition, self-supporting electrodes and nanoparticle structure electrodes have defects in the control of micro-nano structures on the surface of the electrode, and there is randomness in the preparation process, making it difficult to construct ideal electrode structures according to precise design, thereby affecting the stability and repeatability of electrode performance.

[0005] Based on the above shortcomings of the existing technology, it is urgent to develop a new type of electrode structure and preparation method that can effectively solve the problems of bubble adhesion, precise control of bubbles, and reduction of preparation cost and process complexity. SUMMARY

[0006] To solve the above technical problems, the application provides a preparation method of a micro-cone array electrode structure for active ejection separation of catalytic interface bubbles.

[0007] The application provides a preparation method of a micro-cone array electrode structure for catalytic interface bubble active ejection separation, and aims to solve the problem of hydrogen bubble hindering the reaction in water electrolysis hydrogen production. The electrode substrate and the micro-cone array structure are prepared by using surface projection micro-stereolithography 3D printing technology, and the catalytic performance of water electrolysis hydrogen production is given to the electrode substrate by chemical deposition. The chemical deposition can realize self-defined deposition of the catalytic material according to the experiment required and the experimental environment. The bubble on the micro-cone array electrode is subjected to the force generated by the interface between the bubble and the micro-cone electrode surface, that is, the upward combined force of the bubble driving force and the buoyancy, so as to drive the bubble to be ejected upward between the micro-cones, and then to realize the active ejection separation. At the same time, in the process of upward ejection, the bubble is pulled in the vertical plane, and there are different bubble radii between the upper and lower bubbles, and the vertical upward Laplace pressure is generated at the same time, so that the bubble is accelerated to be ejected upward. This processing method is convenient for processing and molding, and the principle is simple. The size of the bubble can be controlled by changing the structure size (micro-cone height, geometric center distance, bottom diameter and other geometric sizes) of the micro-cone, and the ejection separation of all bubbles is realized, so as to promote the ion exchange in the water electrolysis hydrogen production reaction and accelerate the efficient progress of the water electrolysis hydrogen production reaction.

[0008] A preparation method of a micro-cone array electrode structure for catalytic interface bubble active ejection separation, specifically completed by the following steps:

[0009] I. A three-dimensional model of the micro-cone array electrode structure for catalytic interface bubble active ejection separation is established by using a three-dimensional modeling software; the micro-cone array electrode structure for catalytic interface bubble active ejection separation is composed of an electrode bottom plate and a plurality of micro-cone structures;

[0010] The electrode bottom plate in step one is a cuboid or a cylinder;

[0011] The micro-cone structure in step one is a cone or a polygonal pyramid; the circumscribed circle of the bottom section shape of the micro-cone structure is tangent; the bottom of the micro-cone structure is transitioned through a round corner;

[0012] II. The three-dimensional model is image-processed by using a corresponding slice software, and the processed model is transmitted into the control system of a light-curing 3D printer;

[0013] III. The electrode bottom plate is printed by using the light-curing 3D printer, and the micro-cone array electrode structure is obtained by layer-by-layer printing on the electrode bottom plate;

[0014] IV. The printed micro-cone array electrode structure is post-processed by using a 405 nm ultraviolet lamp to obtain the solidified micro-cone array electrode structure;

[0015] V. The solidified micro-cone array electrode structure is soaked and oscillated in a hydrochloric acid solution, and the hydrochloric acid treated micro-cone array electrode structure is obtained after drying;

[0016] Six, the micro-taper array electrode structure treated with hydrochloric acid is subjected to hydrophilic treatment by adopting oxygen plasma, and the micro-taper array electrode structure treated with hydrophilic treatment is obtained after drying;

[0017] Seven, the nickel-based alloy catalyst is deposited on the micro-taper array electrode structure treated with hydrophilic treatment by using chemical plating, and the micro-taper array electrode structure for catalytic interface bubble active ejection separation is obtained after drying.

[0018] The working process of the micro-taper array electrode structure for catalytic interface bubble active ejection separation in the application is as follows:

[0019] In a three-electrode electrolysis environment, the working electrode, i.e., the micro-taper array electrode structure for catalytic interface bubble active ejection separation, is powered, and bubbles are generated on the micro-taper electrode. The micro-bubbles generated at the top actively and rapidly detach upward under the action of bubble driving force and buoyancy. The bubbles generated at the bottom of the micro-taper electrode need to go through the stages of nucleation, aggregation, growth and expansion. After the bubbles expand, they are adsorbed on the adjacent four micro-taper structures and move upward rapidly under the action of bubble driving force, buoyancy, inertial force and other forces. In this process, the bubbles present an asymmetric structure in the vertical plane and generate Laplace pressure difference, so the bubbles accelerate upward in the vertical direction and are actively ejected and separated at the tip of the micro-taper.

[0020] The operation of step six of the application modifies the surface to be super-hydrophilic, which facilitates the attachment of the solution to the electrode surface during the later chemical deposition.

[0021] Compared with the prior art, the technical scheme of the application has the following beneficial effects:

[0022] One, the bubble active ejection separation micro-taper array electrode can realize the ejection separation of all hydrogen bubbles generated on the micro-taper catalytic surface and realize the bubble cleaning of the catalytic interface, relying on the resultant force of adjacent micro-tapers.

[0023] Two, the bubble active ejection separation micro-taper array electrode shows excellent hydrogen production stability and a bubble coverage rate of less than 5% after long-term electrolysis water hydrogen production test.

[0024] Three, the catalyst material of the bubble active ejection separation micro-taper array electrode can be deposited according to the electrolysis water hydrogen production acid-base environment and performance.

[0025] Four, the bubble active ejection separation micro-taper array electrode can control the size and ejection detachment time of hydrogen bubbles by using the geometric dimensions such as micro-taper height, geometric center distance and bottom diameter.

[0026] V. The bubble active ejection separation micro-cone array electrode structure is simple in structure, integrally formed by using surface projection micro-stereolithography 3D printing technology, and is convenient for processing and forming. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 A structural schematic diagram of the bubble active ejection separation micro-cone array electrode structure of the catalytic interface in Example 1, in which 1 is a micro-cone structure, and 2 is an electrode bottom plate;

[0028] Figure 2 A sectional view of the micro-cone structure, in which 3 is a polymer photocured resin, and 4 is a nickel-based alloy catalyst;

[0029] Figure 3 A three-dimensional structure actual photograph of the bubble active ejection separation micro-cone array electrode structure of the catalytic interface in Example 1;

[0030] Figure 4 A scanning electron microscope photograph of the bubble active ejection separation micro-cone array electrode structure of the catalytic interface in Example 1;

[0031] Figure 5 An electrolytic hydrogen production and bubble control experiment process diagram of a bubble active ejection separation micro-cone array electrode structure of the catalytic interface prepared by using Example 1;

[0032] Figure 6 An effect comparison diagram of electrolytic water hydrogen production of a nickel-based carbon paper, a nickel foam and the micro-cone array electrode structure of Example. DETAILED DESCRIPTION

[0033] Specific implementation method one: in combination with the drawing, the preparation method of the bubble active ejection separation micro-cone array electrode structure of the catalytic interface in the embodiment is specifically completed according to the following steps:

[0034] I. A three-dimensional model of the bubble active ejection separation micro-cone array electrode structure of the catalytic interface is established by using three-dimensional modeling software; the bubble active ejection separation micro-cone array electrode structure of the catalytic interface is composed of an electrode bottom plate and a plurality of micro-cone structures;

[0035] The electrode bottom plate in step one is a cuboid or a cylinder;

[0036] The micro-cone structure in step one is a circular cone or a polygonal pyramid; the circumscribed circle of the bottom section shape of the micro-cone structure is tangent; the bottom of the micro-cone structure is transitioned through a round corner;

[0037] II. The three-dimensional model is image-processed by using corresponding slice software, and the processed model is transmitted into the control system of a photocured 3D printer;

[0038] Three, print the electrode base plate using the light-cured 3D printer, and print layer by layer on the electrode base plate to obtain the micro-pyramid array electrode structure;

[0039] Four, use a 405nm ultraviolet lamp to post-process the printed micro-pyramid array electrode structure to obtain the cured micro-pyramid array electrode structure;

[0040] Five, immerse and oscillate the cured micro-pyramid array electrode structure in a hydrochloric acid solution, and obtain the hydrochloric acid treated micro-pyramid array electrode structure after drying;

[0041] Six, use oxygen plasma to perform hydrophilic treatment on the hydrochloric acid treated micro-pyramid array electrode structure, and obtain the hydrophilic treated micro-pyramid array electrode structure after drying;

[0042] Seven, use chemical plating to deposit a nickel-based alloy catalyst on the hydrophilic treated micro-pyramid array electrode structure, and obtain the catalytic interface bubble active ejection separation micro-pyramid array electrode structure after drying.

[0043] The micro-pyramid structure of the present embodiment can change the attachment mode of the bubble on the electrode surface. Compared with the existing electrode structure, the shape of the micro-pyramid makes it difficult for the bubble to stably adhere to its surface. When the bubble is generated, the inclined surface and sharp tip of the micro-pyramid will facilitate the bubble to detach from the electrode surface more easily, reducing the attachment time of the bubble on the electrode surface and reducing the hindrance of the bubble to the contact of the electrode and the electrolyte. In the preparation process, oxygen plasma is used for hydrophilic treatment; the micro-pyramid array electrode surface after hydrophilic treatment has better hydrophilicity; this means that water can spread more easily on the electrode surface, and the adhesion of the bubble on the surface with good hydrophilicity will be weakened. Hydrophilic treatment changes the properties of the electrode surface from hydrophobicity (bubble easy to adhere) to hydrophilicity (bubble not easy to adhere), further solving the problem of bubble adhesion.

[0044] Specific embodiment two: the difference between this embodiment and specific embodiment one is that the polygonal pyramid in step one is a triangular pyramid or a rectangular pyramid. The others are the same as specific embodiment one.

[0045] Specific embodiment three: the difference between this embodiment and specific embodiment one is that the circumscribed circle diameter of the bottom cross-sectional shape of the micro-pyramid structure in step one ranges from 50 to 300μm. The others are the same as specific embodiment one.

[0046] Specific embodiment four: the difference between this embodiment and specific embodiment one is that the height of the micro-pyramid structure in step one is 100-500μm. The others are the same as specific embodiment one.

[0047] Embodiment five: different from embodiment one is that the distance between the geometric centers of the adjacent micro-cone structures in step one is 70-130 μm. The rest is the same as embodiment one.

[0048] Embodiment six: different from embodiment one is that the material of the electrode base plate in step one is high-molecular photo-cured resin; the material of the micro-cone structure is high-molecular photo-cured resin. The rest is the same as embodiment one.

[0049] Embodiment seven: different from embodiment one is that the time of the post-processing in step four is 3-5 min. The rest is the same as embodiment one.

[0050] Embodiment eight: different from embodiment one is that the concentration of the hydrochloric acid in step five is 0.1 mol / L; the soaking time is 10-15 min. The rest is the same as embodiment one.

[0051] Embodiment nine: different from embodiment one is that the hydrophilic treatment in step six is that the micro-cone array electrode structure after the hydrochloric acid treatment is placed on a glass slide, and a hand-held oxygen plasma processor is used to perform 10 min reciprocating cycle bombardment treatment on the micro-cone array electrode structure after the hydrochloric acid treatment; the frequency of the hand-held oxygen plasma processor is 4 MHz, and the output voltage is 30000 V. The rest is the same as embodiment one.

[0052] Embodiment ten: different from embodiment one is that the step seven of depositing the nickel-based alloy catalyst on the micro-cone array electrode structure after the hydrophilic treatment is performed according to the following steps:

[0053] I. A solution is configured by 50 mL of DI, 500 μL of concentrated hydrochloric acid, and 0.564 g of SnCl2, and a heating platform is used to heat the solution to 40℃, and then the micro-cone array electrode structure is immersed in the solution for 10 min, while a magnetic stirrer is used to stir the solution to ensure liquid circulation; then the micro-cone array electrode structure is repeatedly rinsed with DI for three to five times, and dried in a drying box; then, the micro-cone array electrode structure is placed in an activation solution composed of 50 mL of DI, 200 μL of concentrated hydrochloric acid with a mass fraction of 37%, and 0.008 g of PbCl2, heated at 50℃ for 20 min to complete the activation process, to obtain the activated micro-cone array electrode structure;

[0054] II. 0.7275 g of NiSO4·6H2O is added to a beaker containing 60 mL of deionized water, the container is placed on a heating table at 70°C, and the solute in the beaker is completely dissolved with a magnetic stirrer; then 1.25 g of C6H8O7·H2O is added to the beaker, and stirring is continuously performed; then the pH value of the plating solution is adjusted to 9-10 by adding NH3·H2O dropwise into the beaker; finally, 0.64 g of NaPO2H2·H2O is added, and the plating solution is fully stirred; the activated micro-taper array electrode structure is placed in the plating solution for deposition for 5 min, and is cleaned with DI, and is naturally dried. The other parts are the same as in Embodiment I.

[0055] The beneficial effects of the present application are verified by using the following embodiments:

[0056] Embodiment 1: Combination Figures 1-5 In this embodiment, the preparation method of the micro-taper array electrode structure for catalytic interface bubble active ejection separation is described, which is completed according to the following steps:

[0057] I. A three-dimensional modeling software is used to establish a three-dimensional model of the micro-taper array electrode structure for catalytic interface bubble active ejection separation; the micro-taper array electrode structure for catalytic interface bubble active ejection separation is composed of an electrode bottom plate and a plurality of micro-taper structures;

[0058] The electrode bottom plate in step I is a cuboid;

[0059] The micro-taper structure in step I is a circular cone; the circumscribed circle of the bottom cross-sectional shape of the micro-taper structure is tangent; the bottom of the micro-taper structure is transitioned through a round corner; the diameter of the circumscribed circle of the bottom cross-sectional shape of the micro-taper structure ranges from 100 μm; the height of the micro-taper structure is 300 μm; the geometric center distance of adjacent micro-taper structures is 100 μm; the material of the electrode bottom plate and the micro-taper structure is HTL resin of Mofang Precision Company;

[0060] II. The three-dimensional model is image-processed by using corresponding slicing software, and the processed model is transmitted into the control system of a light-curing 3D printer;

[0061] III. The electrode bottom plate is printed by using the light-curing 3D printer, and the micro-taper array electrode structure is obtained through layer-by-layer printing on the electrode bottom plate;

[0062] IV. The printed micro-taper array electrode structure is irradiated by a 405 nm ultraviolet lamp for 3-5 min to obtain the cured micro-taper array electrode structure;

[0063] V. The cured micro-taper array electrode structure is soaked and oscillated in a hydrochloric acid solution with a concentration of 0.1 mol / L for 10 min, and is dried for 10 min to obtain the hydrochloric acid treated micro-taper array electrode structure;

[0064] Six, the micro-taper array electrode structure after hydrochloric acid treatment is subjected to hydrophilic treatment for 10 min by using oxygen plasma, and the hydrophilic treated micro-taper array electrode structure is obtained after drying for 10 min;

[0065] The hydrophilic treatment is that the micro-taper array electrode structure after hydrochloric acid treatment is placed on a glass slide, and the micro-taper array electrode structure after hydrochloric acid treatment is subjected to 10 min reciprocating cycle bombardment treatment by using a handheld oxygen plasma processor; the frequency of the handheld oxygen plasma processor is 4 MHz, and the output voltage is 30000 V;

[0066] Seven, the nickel-based alloy catalyst is deposited on the micro-taper array electrode structure after hydrophilic treatment by using chemical plating, and the catalytic interface bubble active type ejection separation micro-taper array electrode structure is obtained after drying;

[0067] The nickel-based alloy catalyst is deposited on the micro-taper array electrode structure after hydrophilic treatment by using chemical plating, and the catalytic interface bubble active type ejection separation micro-taper array electrode structure is obtained after drying;

[0068] One, a solution composed of 50 mL DI, 500 μL concentrated hydrochloric acid and 0.564 g SnCl2 is configured, and the solution is heated to 40°C using a heating platform, then the micro-taper array electrode structure is immersed in the solution for 10 min, while the solution is stirred with a magnetic stirrer to ensure liquid circulation; then the micro-taper array electrode structure is repeatedly rinsed with DI for three to five times, and dried in a drying box; then, the micro-taper array electrode structure is placed in an activation solution composed of 50 mL DI, 200 μL concentrated hydrochloric acid with a mass fraction of 37% and 0.008 g PbCl2, and heated at 50°C for 20 min to complete the activation process, to obtain the activated micro-taper array electrode structure;

[0069] Two, 0.7275 g of NiSO4·6H2O is added to a beaker containing 60 mL of deionized water, and the container is placed on a heating table at 70°C, while the solute in the beaker is completely dissolved by using a magnetic stirrer; then 1.25 g of C6H8O7·H2O is added to the beaker, and the stirring is continued; then the pH value of the plating solution is adjusted to 9-10 by adding NH3·H2O dropwise to the beaker; finally, 0.64 g of NaPO2H2·H2O is added, and the plating solution is fully stirred; the activated micro-taper array electrode structure is placed in the plating solution for deposition for 5 min, and then rinsed with DI and naturally dried.

[0070] Electrolytic water hydrogen production:

[0071] In a three-electrode electrolysis environment, the catalytic interface bubble active ejection separation micro-cone array electrode structure is placed in a three-electrode electrolysis hydrogen production acid electrolytic cell, and 0.1 mol / L sulfuric acid solution is added to the electrolytic cell. The catalytic interface bubble active ejection separation micro-cone array electrode structure is used as the working electrode, graphite is used as the counter electrode, and silver / silver chloride is used as the reference electrode. After using a constant voltage of 2V to power on, bubbles are generated on the micro-needle electrode, and the small bubbles generated at the top are actively and rapidly separated upward under the action of bubble driving force and buoyancy. The bubbles generated at the bottom of the micro-cone electrode need to go through the stages of nucleation, aggregation, growth, and expansion, and after the bubble expands, it will be adsorbed on the adjacent four micro-cone structures under the action of bubble driving force, buoyancy, inertial force and other forces, and move upward rapidly. During this process, the bubble presents an asymmetric structure in the vertical plane and generates Laplace pressure, so the bubble accelerates upward in the vertical direction and is actively ejected and separated at the tip of the micro-cone.

[0072] Figure 4 It is a scanning electron microscope image of the catalytic interface bubble active ejection separation micro-cone array electrode structure in Example 1.

[0073] Figure 5 It is an electrolytic hydrogen production and bubble control experiment process diagram of a catalytic interface bubble active ejection separation micro-cone array electrode structure prepared by Example 1.

[0074] From Figures 4-5 It can be seen that a catalytic interface bubble active ejection separation micro-cone array electrode structure can produce hydrogen.

[0075] Figure 6 It is an electrolytic water hydrogen production effect comparison diagram of nickel-based carbon paper, nickel foam, and Example micro-cone array electrode structure. Under the same electrolysis environment and the same 2V constant voltage, the current density of the 3D micro-cone electrode is stably at 116mAcm -2 , which is 2.7 times the current density of nickel-based carbon paper and 1.51 times the current density of nickel foam electrode. Therefore, the 3D micro-cone electrode shows more excellent bubble control ability and "cleaning" ability of the electrode surface catalytic area, thereby having greater catalytic performance in electrolytic hydrogen production.

Claims

1. A method for preparing a microconical array electrode structure for active ejection separation of bubbles at a catalytic interface, characterized in that... The preparation method is specifically carried out according to the following steps:

1. A three-dimensional model of the microcone array electrode structure for active ejection separation of bubbles at the catalytic interface is established using three-dimensional modeling software; the microcone array electrode structure for active ejection separation of bubbles at the catalytic interface consists of an electrode base plate and several microcone structures; The electrode base plate mentioned in step one is a cuboid or a cylinder; The microconical structure described in step one is a cone or a polygonal pyramid; the circumscribed circle of the bottom cross-section of the microconical structure is tangent to the microconical structure; the bottom of the microconical structure is transitioned by rounded corners; the diameter of the circumscribed circle of the bottom cross-section of the microconical structure ranges from 50 to 300 μm; the height of the microconical structure is from 100 to 500 μm. The geometric center distance between adjacent microconical structures is 70–130 μm; 2. Use the corresponding slicing software to process the image of the 3D model, and then transfer the processed model into the control system of the photopolymer 3D printer; 3. Use a photopolymer 3D printer to print an electrode base plate, and then print layer by layer on the electrode base plate to obtain a microcone array electrode structure. IV. The printed microcone array electrode structure was post-processed using a 405nm ultraviolet lamp to obtain the cured microcone array electrode structure.

5. The cured microcone array electrode structure is immersed in hydrochloric acid solution and shaken, and then dried to obtain the hydrochloric acid-treated microcone array electrode structure. VI. The hydrophilic treatment of the hydrochloric acid-treated microcone array electrode structure is carried out by oxygen plasma, and the hydrophilic treatment microcone array electrode structure is obtained after drying. The hydrophilic treatment is carried out by placing the hydrochloric acid-treated microcone array electrode structure on a glass slide and using a handheld oxygen plasma processor to perform a 10-minute reciprocating cyclic bombardment treatment on the hydrochloric acid-treated microcone array electrode structure. The handheld oxygen plasma processor has a frequency of 4MHz and an output voltage of 30000V; 7. A nickel-based alloy catalyst is deposited on a hydrophilically treated microconical array electrode structure using chemical plating. After drying, a microconical array electrode structure with active ejection separation of bubbles at the catalytic interface is obtained.

2. The method for preparing a microconical array electrode structure for active ejection separation of bubbles at a catalytic interface according to claim 1, characterized in that... The polygonal pyramid mentioned in step one is a triangular pyramid or a rectangular pyramid.

3. The method for preparing a microconical array electrode structure for active ejection separation of bubbles at a catalytic interface according to claim 1, characterized in that... The electrode substrate in step one is made of photopolymer resin; the microconical structure is also made of photopolymer resin.

4. The method for preparing a microconical array electrode structure for active ejection separation of bubbles at a catalytic interface according to claim 1, characterized in that... The post-processing time described in step four is 3 to 5 minutes.

5. The method for preparing a microconical array electrode structure for active ejection separation of bubbles at a catalytic interface according to claim 1, characterized in that... The concentration of hydrochloric acid mentioned in step five is 0.1 mol / L; the soaking time is 10-15 min.

6. The method for preparing a microconical array electrode structure for active ejection separation of bubbles at a catalytic interface according to claim 1, characterized in that... Step seven involves using electroless plating to deposit the nickel-based alloy catalyst onto the hydrophilically treated microcone array electrode structure, specifically as follows:

1. Prepare a solution consisting of 50 mL DI, 500 μL concentrated hydrochloric acid, and 0.564 g SnCl2, and heat the solution to 40 °C using a heating platform. Then, immerse the microcone array electrode structure in this solution for 10 min while stirring the solution with a magnetic stirrer to ensure liquid circulation. Next, rinse the microcone array electrode structure repeatedly with DI three to five times and dry it in a drying oven. Then, place the microcone array electrode structure in an activation solution consisting of 50 mL DI, 200 μL concentrated hydrochloric acid (37% by mass), and 0.008 g PbCl2, and heat it at 50 °C for 20 min to complete the activation process, obtaining the activated microcone array electrode structure.

2. Add 0.7275g NiSO4·6H2O to a beaker containing 60mL deionized water. Place the container on a 70℃ heating plate and use a magnetic stirrer to completely dissolve the solute in the beaker. Then add 1.25g C6H8O7·H2O to the beaker and stir continuously. Next, adjust the pH of the plating solution to 9-10 by adding NH3·H2O dropwise to the beaker. Finally, add 0.64g NaPO2H2·H2O and stir the plating solution thoroughly. Place the activated microcone array electrode structure into the plating solution for 5 minutes, rinse with DI, and allow it to dry naturally.

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