Metal / nano array heterostructure electrode prepared through oxidation corrosion and method
The preparation of metal/nanoarray heterostructure electrodes by oxidative corrosion method solves the problems of complex and long synthesis process of existing electrocatalysts, realizes efficient and low-cost electrocatalyst preparation, and improves the catalytic performance of electrode materials.
Patent Information
- Application Number
- CN202511360690.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-23
- Publication Date
- 2025-12-16
AI Technical Summary
Existing electrocatalyst synthesis processes are characterized by complexity, long preparation cycles, high costs, and the inability to achieve a balance between performance and cost.
Metal/nanoarray heterostructure electrodes were prepared by an oxidation corrosion method. The precursor was immersed in an acidic solution and sulfur powder was chemically vapor-deposited. Then, it was immersed in a hydrogen peroxide solution for oxidation corrosion to generate the metal/nanoarray heterostructure electrode.
The process of producing nanostructures has been simplified, the preparation cycle has been shortened, the cost has been reduced, and the electrocatalytic activity and catalytic performance of electrode materials have been significantly improved.
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Figure CN121137652A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of electrocatalyst preparation, in particular to a metal / nanometer array heterostructure electrode prepared by oxidation corrosion and a method thereof. BACKGROUND
[0002] Electrocatalytic water splitting is an important method for continuously generating hydrogen energy in water, which includes oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). In order to reduce the electrical energy consumption on both sides of OER and HER, it is an important and challenging task to develop efficient electrocatalysts.
[0003] Currently, the main electrocatalysts for OER and HER are noble metal catalysts, including Pt, Ir / Ru-based oxides, etc. Although these catalysts have high catalytic activity, their high cost and scarce reserves limit their application. The current research significance is to develop transition metal-based electrocatalysts with low cost, high efficiency and abundant reserves. An effective method to improve the electrocatalytic performance is to optimize the electrochemical reaction on the surface or interface of the material by morphology engineering and construction of active sites. One effective strategy is to increase the specific surface area by preparing and regulating three-dimensional nanostructures, which is conducive to promoting electron transfer and ion diffusion, and ultimately improving the electrocatalytic activity. The common method to make a working electrode is to cover a powder material coating with certain nanostructure on a conductive substrate. However, in recent years, researchers have adopted a solution thermal method to achieve in-situ generation of nanostructures, thereby preparing electrode materials in a self-supporting system. By using this method, the use of organic binders can be avoided, the contact resistance can be reduced, and more active sites and enhanced structural stability can be provided. However, despite this, the relative complexity of the synthesis process still results in a long period for preparing catalyst electrodes, usually requiring tens of hours or even longer. In addition, considering that most semiconductor compound nanometer arrays have low conductivity, further research is needed in terms of catalyst performance, synthesis period and energy consumption. SUMMARY
[0004] The problem solved by the present application is at least one of the following aspects of the existing electrocatalyst synthesis process: complexity, long preparation period, high cost and performance compromise.
[0005] To solve the above problems, the present application provides a method for preparing a metal / nanometer array heterostructure electrode by oxidation corrosion, comprising the following steps: Step S1: immerse the precursor in an acidic solution, then take it out, deposit sulfur powder on the surface of the precursor by chemical vapor deposition, and naturally cool in the furnace to obtain the activated precursor; Step S2: the activated precursor of step S1 is immersed in a hydrogen peroxide solution, and after taking out, it is cleaned to obtain an oxidized etching prepared metal / nano-array heterostructure electrode material.
[0006] Further, in step S1, the precursor is one of foamed iron, foamed nickel, foamed cobalt and foamed copper.
[0007] Further, in step S1, the acid solution is one of dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid.
[0008] Further, in step S1, the immersion time of the precursor in the acid solution is 30s-60s.
[0009] Further, in step S1, the temperature during the chemical vapor deposition of sulfur powder is 200-600℃.
[0010] Further, in step S1, the duration of the chemical vapor deposition is 10 min-2 h.
[0011] Further, in step S2, the mass concentration percentage of the hydrogen peroxide solution is 0.1%-30%.
[0012] Further, in step S2, the time for the activated precursor to be immersed in the hydrogen peroxide solution is 1s-60s.
[0013] The method for preparing a metal / nano-array heterostructure electrode by oxidized etching according to the present application has the following advantages over the prior art: 1. The method for preparing a metal / nano-array heterostructure electrocatalyst based on oxidized etching simplifies the production process of nanostructures, and can form a nano-array by etching within a few minutes, which is efficient and short in cycle; 2. The preparation method of the present application can generate a metal / three-dimensional cross-linked flaky nano-array heterostructure at low cost and quickly, optimize the charge conduction path, significantly increase the number of active sites, and thus improve the catalytic activity of the electrode material; 3. The present application utilizes the natural high oxidation of hydrogen peroxide to oxidize and etch the activated layer of the precursor, and mainly relies on two principles to generate a metal / nano-array structure: (1) the natural oxidation of oxygen is higher than that of sulfur, and under the action of hydrogen peroxide, part of the sulfur elements covered on the surface of the precursor are replaced and removed, especially the electrochemical activity of the grain boundary is higher than that in the grain, and the difference in oxidation corrosion rate between the grain boundary and the grain site causes the precursor surface to produce a rugged morphology; (2) the rugged morphology further increases the contact area between the substrate and the hydrogen peroxide, thereby causing more sufficient oxidation, and the oxidized iron-based compounds generated during the oxidation reaction tend to deposit on the sharp end of the surface protrusions, thereby forming a metal / three-dimensional cross-linked flaky nano-array heterostructure. 4. The electrode structure generated in this invention is a metal substrate / nanoarray heterostructure. The metal substrate has good natural conductivity, which facilitates rapid charge transfer of electrons through the heterostructure interface, thereby enhancing electrocatalytic performance. Self-supporting electrode sheets with a size of approximately 20cm × 20cm can be easily fabricated as needed. Compared to the electrode size of several square centimeters in most existing cases, this greatly expands the fabrication size of the electrode material and improves production safety.
[0014] To address the aforementioned problems, the present invention also provides an oxidative etching method for preparing a metal / nanoarray heterostructure electrode, which is fabricated according to the oxidative etching method described above.
[0015] The advantages of the oxidation corrosion method for preparing metal / nanoarray heterostructure electrodes described in this invention compared to existing technologies are the same as those of the above-mentioned oxidation corrosion method for preparing metal / nanoarray heterostructure electrodes compared to existing technologies, and will not be repeated here. Attached Figure Description
[0016] Figure 1 This is a scanning electron microscope image of the electrocatalyst in Example 1; Figure 2 This is a high-resolution image of the medium-to-large-sized electrode in Example 1. Detailed Implementation
[0017] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
[0018] This invention provides a method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion, comprising the following steps: Step S1: After immersing the precursor in an acidic solution, remove it and deposit sulfur powder onto the surface of the precursor by chemical vapor deposition. Allow it to cool naturally in the furnace to obtain the activated precursor. Step S2: Immerse the activated precursor from step S1 in a hydrogen peroxide solution, remove it, and clean it to obtain the metal / nanoarray heterostructure electrode material prepared by oxidation corrosion.
[0019] The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to the embodiments of the present invention has the following advantages over the prior art: 1. The method for preparing metal / nanoarray heterostructure electrocatalysts based on oxidative corrosion in the embodiments of the present invention simplifies the production process of nanostructures. Nanoarrays can be formed through corrosion within minutes, which is highly efficient and has a short cycle. 2. The preparation method of this invention can generate metal / three-dimensional cross-linked sheet-like nanoarray heterostructures at low cost and quickly, optimize the charge conduction path, significantly increase the number of active sites, and thus improve the catalytic activity of the electrode material; 3. The embodiments of the present invention utilize the high natural oxidizing effect of hydrogen peroxide to oxidize and corrode the activated layer on the surface of the precursor. The metal / nano array structure is mainly generated based on two principles: (1) The natural oxidizing power of oxygen is higher than that of sulfur. Under the action of hydrogen peroxide, part of the sulfur element in the sulfurized layer covering the surface of the precursor is replaced and removed. In particular, the electrochemical activity at the grain boundary is higher than that in the grain. The difference in oxidation and corrosion rate between the grain boundary and the grain interior causes the precursor surface to produce a rugged morphology; (2) The rugged morphology further increases the contact area between the substrate and hydrogen peroxide, thereby triggering a more complete oxidation. The iron oxide-based compounds generated by the oxidation reaction tend to be deposited at the protruding tips of the surface, thereby forming a metal / three-dimensional cross-linked sheet-like nano array heterostructure. 4. The electrode structure generated in the embodiments of the present invention is a metal substrate / nanoarray heterostructure. The metal substrate has good natural conductivity, which is conducive to the rapid charge transfer of electrons through the heterostructure interface, thereby enhancing the electrocatalytic performance. Self-supporting electrode sheets with a size of approximately 20cm × 20cm can be easily prepared as needed. Compared with the electrode size of several square centimeters in most existing cases, this greatly expands the preparation size of electrode materials and improves production safety.
[0020] In some specific embodiments, in step S1, the precursor is one of foamed iron, foamed nickel, foamed cobalt, and foamed copper. Therefore, the range of precursors is wide, and the raw materials are readily available.
[0021] In some specific embodiments, in step S1, the acidic solution is one of dilute hydrochloric acid, dilute nitric acid, or dilute sulfuric acid. Therefore, common acids can be used, the raw materials are readily available, and this simplifies the preparation process.
[0022] In some specific embodiments, in step S1, the immersion time of the precursor in the acidic solution is 30s-60s. This ensures thorough cleaning of the precursor.
[0023] In some specific embodiments, in step S1, the temperature during chemical vapor deposition of sulfur powder is 200-600°C.
[0024] In some specific embodiments, the chemical vapor deposition duration in step S1 is 10 min to 2 h. This ensures that the chemical vapor deposition effect is fully achieved.
[0025] In some specific embodiments, in step S2, the mass concentration percentage of the hydrogen peroxide solution is 0.1%-30%.
[0026] In this embodiment, the oxidation effect of hydrogen peroxide is used to oxidize and corrode the activated layer on the surface of the precursor. Specifically, the metal / nano array structure is generated through two principles: (1) Oxygen has a higher natural oxidizing power than sulfur. Under the action of hydrogen peroxide, part of the sulfur in the sulfurized layer covering the surface of the precursor is replaced and removed. In particular, the electrochemical activity at the grain boundary is higher than that in the grain. The difference in oxidation and corrosion rate between the grain boundary and the grain interior causes the precursor surface to produce a rugged morphology; (2) The rugged morphology further increases the contact area between the substrate and hydrogen peroxide, thereby triggering a more complete oxidation. The iron oxide-based compounds generated by the oxidation reaction tend to deposit at the protruding tips of the surface, thereby forming a metal / three-dimensional cross-linked sheet-like nano array heterostructure. It can be seen that the oxidation effect of hydrogen peroxide is fast and effective, greatly shortening the preparation cycle, and the raw materials are readily available and low in cost.
[0027] In some specific embodiments, in step S2, the activated precursor is immersed in the hydrogen peroxide solution for 1-60 seconds. This ensures that the oxidation effect of the hydrogen peroxide is fully realized.
[0028] The advantages of the oxidation corrosion method for preparing metal / nanoarray heterostructure electrodes described in this invention over the prior art are the same as those of the above-mentioned oxidation corrosion method for preparing metal / nanoarray heterostructure electrodes over the prior art, and will not be repeated here.
[0029] Example 1: This embodiment describes a method for preparing metal / nanoarray heterostructure electrodes through oxidation corrosion, including the following steps: Step S1: Immerse the precursor in HCl solution for 30 seconds; then use a chemical vapor deposition apparatus to place the precursor sheet in the gas inlet, arrange 2.5 g of sublimed sulfur powder upstream, heat to 300°C for 10 minutes, and finally allow it to cool naturally in the furnace to obtain the activated precursor. Step S2: Immerse the surface-activated precursor in hydrogen peroxide solution for 30 seconds. After the immersion, remove and clean it to obtain the metal / nanoarray heterostructure electrode material prepared by oxidation corrosion.
[0030] The precursor mentioned in step S1 is prepared according to the following steps: the precursor is prepared into a size of 10cm×10cm, and then washed successively with 5mol / L HCl solution, deionized water and anhydrous ethanol for 5min each time. The precursor mentioned in step S1 uses foamed iron with a thickness of 2 mm; The hydrogen peroxide mentioned in step S2 is 0.1% by mass.
[0031] Figure 1The image shows a scanning electron microscope (SEM) image of the self-supporting electrocatalyst prepared in Example 1 by hydrogen peroxide corrosion. The image shows that the catalyst prepared by the method of preparing metal / nanoarray heterostructure electrodes by oxidative corrosion exhibits a uniform three-dimensional cross-linked sheet-like nanosurface structure.
[0032] In Example 1, the preparation time was less than 0.5 hours, which effectively improved the production rate and was far superior to the current preparation time of ten to several tens of hours.
[0033] Figure 2 To obtain high-resolution images of large-size electrodes, a precursor with a size greater than 10cm × 10cm was used, resulting in a working surface area of 100cm². 2 This significantly increases the size of the electrode material, compared to the existing electrode size of several square centimeters in most cases.
[0034] Example 2: This embodiment describes a method for preparing metal / nanoarray heterostructure electrodes through oxidation corrosion, including the following steps: Step S1: Immerse the precursor in HCl solution for 30 seconds; then use a chemical vapor deposition apparatus to place the precursor sheet in the gas inlet, arrange 2.5 g of sublimed sulfur powder upstream, heat to 400°C for 10 minutes, and finally allow it to cool naturally in the furnace to obtain the activated precursor. Step S2: Immerse the surface-activated precursor in hydrogen peroxide solution for 10 seconds. After immersion, remove and clean to obtain the metal / nanoarray heterostructure electrode material prepared by oxidation corrosion.
[0035] The precursor mentioned in step S1 is prepared according to the following steps: the precursor is prepared into a size of 5cm×5cm, and then washed successively with 5mol / L HCl solution, deionized water and anhydrous ethanol for 5min each time. The precursor mentioned in step S1 uses foamed iron with a thickness of 2 mm; The hydrogen peroxide mentioned in step S2 is 1% by mass.
[0036] Example 3: This embodiment describes a method for preparing metal / nanoarray heterostructure electrodes through oxidation corrosion, including the following steps: Step S1: Immerse the precursor in HCl solution for 30 seconds; then use a chemical vapor deposition apparatus to place the precursor sheet in the gas inlet, arrange 2.5 g of sublimed sulfur powder upstream, heat to 300°C for 15 minutes, and finally allow it to cool naturally in the furnace to obtain the activated precursor. Step S2: Immerse the surface-activated precursor in hydrogen peroxide solution for 40 seconds. After the immersion, remove and clean it to obtain the metal / nanoarray heterostructure electrode material prepared by oxidation corrosion.
[0037] The precursor mentioned in step S1 is prepared according to the following steps: the precursor is prepared into a size of 15cm×15cm, and then washed successively with 5mol / L HCl solution, deionized water and anhydrous ethanol for 5min each time. The precursor mentioned in step S1 uses foamed iron with a thickness of 2 mm; The hydrogen peroxide used in step S2 is 5% by mass.
[0038] Example 4: This embodiment describes a method for preparing metal / nanoarray heterostructure electrodes through oxidation corrosion, including the following steps: Step S1: Immerse the precursor in HCl solution for 30 seconds; then use a chemical vapor deposition apparatus to place the precursor sheet in the gas inlet, arrange 2.5 g of sublimed sulfur powder upstream, heat to 300°C for 15 minutes, and finally allow it to cool naturally in the furnace to obtain the activated precursor. Step S2: Immerse the surface-activated precursor in hydrogen peroxide solution for 40 seconds. After the immersion, remove and clean it to obtain the metal / nanoarray heterostructure electrode material prepared by oxidation corrosion.
[0039] The precursor mentioned in step S1 is prepared according to the following steps: the precursor is prepared into a size of 20cm×20cm, and then washed successively with 5mol / L HCl solution, deionized water and anhydrous ethanol for 5min each time. The precursor mentioned in step S1 uses foamed iron with a thickness of 2 mm; The hydrogen peroxide mentioned in step S2 is 10% by mass.
[0040] While the present invention has been disclosed above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and all such changes and modifications will fall within the scope of protection of the present invention.
Claims
1. A method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion, characterized in that, Includes the following steps: Step S1: After immersing the precursor in an acidic solution, remove it and deposit sulfur powder onto the surface of the precursor by chemical vapor deposition. Allow it to cool naturally in the furnace to obtain the activated precursor. Step S2: Immerse the activated precursor from step S1 in a hydrogen peroxide solution, remove it, and clean it to obtain the metal / nanoarray heterostructure electrode material prepared by oxidation corrosion.
2. The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to claim 1, characterized in that, In step S1, the precursor is one of foamed iron, foamed nickel, foamed cobalt, and foamed copper.
3. The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to claim 1, characterized in that, In step S1, the acidic solution is one of dilute hydrochloric acid, dilute nitric acid, or dilute sulfuric acid.
4. The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to claim 1, characterized in that, In step S1, the immersion time of the precursor in the acidic solution is 30s-60s.
5. The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to claim 1, characterized in that, In step S1, the temperature during the chemical vapor deposition of sulfur powder is 200-600℃.
6. The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to claim 5, characterized in that, In step S1, the chemical vapor deposition lasts for 10 min to 2 h.
7. The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to claim 1, characterized in that, In step S2, the mass concentration percentage of the hydrogen peroxide solution is 0.1%-30%.
8. The method for preparing metal / nanoarray heterostructure electrodes by oxidation corrosion according to claim 7, characterized in that, In step S2, the activated precursor is immersed in the hydrogen peroxide solution for 1s-60s.
9. A method for preparing a metal / nanoarray heterostructure electrode using oxidation corrosion, characterized in that, It is prepared by the method of preparing metal / nanoarray heterostructure electrode by oxidation corrosion according to any one of claims 1 to 9.