Preparation method of electrolytic seawater-resistant chlorine corrosion heterogeneous catalytic anode electrode
By constructing a nickel-iron nanosheet array catalyst on the surface of a metal foam, the problem of chloride ion corrosion in seawater was solved, achieving efficient oxygen evolution reaction and stable electrodes, thus supporting the supply of green electricity.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NORTH CHINA ELECTRIC POWER UNIV
- Filing Date
- 2024-11-29
- Publication Date
- 2026-05-29
Smart Images
Figure CN122105475A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of advanced nanomaterials technology, specifically relating to a method for preparing a heterogeneous catalytic anode electrode for chlorine corrosion resistance in seawater electrolysis. Background Technology
[0002] Energy and environmental issues are compelling green, zero-carbon hydrogen energy to become a key direction for future energy development. Hydrogen production through water electrolysis is widely considered the most promising key technology. However, commercial water electrolysis typically requires highly purified water, placing enormous pressure on water resources. Since seawater accounts for 96.5% of the Earth's total water volume and is a virtually inexhaustible resource, "deriving water from the sea" will become an important direction for hydrogen energy development.
[0003] Combining seawater electrolysis with coastal solar and offshore wind power could be a significant breakthrough in renewable energy-based hydrogen production technology, enabling flexible energy conversion and storage while eliminating the volatility of renewable energy sources.
[0004] However, the presence of approximately 0.5 M chloride ions in seawater competes with the oxygen evolution reaction (OER) for the chloride evolution reaction (CER), which not only affects the selectivity of the OER but may also lead to electrode corrosion and failure. Therefore, developing anode materials with excellent resistance to chloride corrosion and efficient OER catalytic performance has become a key challenge for seawater electrolysis technology. Summary of the Invention
[0005] This invention aims to provide a method for preparing a heterogeneous catalytic anode electrode resistant to chloride corrosion in seawater electrolysis. This method effectively prevents chloride ion corrosion by selecting specific anode materials for alkaline simulated seawater electrolysis, while also exhibiting excellent oxygen evolution reaction activity and stability.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] The preparation method of the heterogeneous catalytic anode for chlorine corrosion resistance in seawater electrolysis provided by this invention can be achieved through the following technical route: Step 1, metal foam cleaning treatment: Cut the metal foam into appropriate sizes, immerse it in hydrochloric acid aqueous solution, anhydrous ethanol, and deionized water respectively for ultrasonic treatment, and then dry it for later use. Step 2, preparation of nickel-iron-based metal-organic framework precursor: Weigh nickel salt and iron salt and dissolve them in a solvent to form solution A; dissolve the organic ligand in the solvent to form solution B; stir and mix solutions A and B uniformly at 60°C to form solution C; place the metal foam and solution C in a hydrothermal reactor for hydrothermal reaction to obtain the nickel-iron-based metal-organic framework precursor. Step 3, synthesis of nickel-iron-based porous carbon heterostructure electrode: Rinse and dry the nickel-iron-based metal-organic framework precursor to obtain the nickel-iron-based porous carbon heterostructure electrode.
[0008] Furthermore, the solvent in solution A is one or both of deionized water and formamide, wherein the volume ratio of deionized water to formamide is 1:10 to 10:1.
[0009] Furthermore, the solvent in solution B is one or more of deionized water, methanol, and ethanol.
[0010] Furthermore, the organic ligand in solution B is an organic amine.
[0011] Furthermore, the molar ratio of nickel salt to iron salt is 1:10 to 10:1; the total molar concentration of metal salt in solution A is 10 to 100 mM; and the molar ratio of organic ligand to total metal salt is 5:1 to 1:5.
[0012] Furthermore, the metal foam includes: aluminum foam, nickel foam, and titanium foam.
[0013] Furthermore, the hydrothermal reaction temperature is 100–200°C, and the reaction time is 10–60 h.
[0014] Furthermore, the electrocatalyst channel contains amine groups to inhibit Cl- corrosion and exhibits excellent oxygen evolution reaction selectivity in alkaline simulated seawater electrolysis.
[0015] Compared with the prior art, the present invention has the following beneficial effects:
[0016] 1. This invention relates to a method for preparing a heterogeneous catalytic anode electrode for chlorine corrosion resistance in seawater electrolysis. A nickel-iron nanosheet structure is constructed in situ on the surface of a metal foam via a hydrothermal reaction. The surface is then modified with organic molecules to obtain a nickel-iron nanosheet array catalyst with a porous carbon heterostructure. The nanosheet structure and porous carbon facilitate rapid diffusion of oxygen and electrolyte, while simultaneously exposing numerous active sites, thus improving catalytic efficiency. During the oxygen evolution reaction, the amino-containing porous carbon on the surface forms coordination bonds with the metal surface, constructing a stable adsorption layer that prevents chloride ions from directly contacting the metal surface, effectively inhibiting chlorine corrosion.
[0017] 2. This invention relates to a method for preparing a heterogeneous catalytic anode electrode for chlorine corrosion resistance in seawater electrolysis, providing an efficient and clean hydrogen production pathway, offering flexible energy conversion and storage solutions for solar and offshore wind energy in coastal areas, effectively eliminating the volatility of renewable energy, and providing strong technical support for the stable supply of green electricity. Attached Figure Description
[0018] To illustrate the implementation or technical solution of the present invention in more detail and intuitively, the accompanying drawings used in the implementation or technical solution are described below. Other embodiments obtained by those skilled in the art are all within the scope of protection of the present invention.
[0019] Figure 1 This is a schematic diagram of the fabrication process of the heterogeneous catalytic electrode of the present invention;
[0020] Figure 2 The results are electrochemical tests of the heterogeneous catalytic electrode prepared in Example 1 of this invention in alkaline simulated seawater, where (a) is a linear sweep voltammetry curve; and (b) is a stability curve of voltage versus time. Detailed Implementation
[0021] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments:
[0022] A method for preparing a heterogeneous catalytic anode resistant to chlorine corrosion in seawater electrolysis includes the following steps:
[0023] A certain amount of nickel and iron salts were dissolved in a mixed solution of deionized water and formamide to prepare solution A. Then, an appropriate amount of ethylamine was dissolved in a mixed solution of methanol and ethanol to obtain solution B. Solutions A and B were ultrasonically homogenized separately and stirred under heating conditions to form solution C. Next, solution C was transferred to a hydrothermal reactor, and a 2*3cm piece of [material name missing] was added. 2 Pretreated nickel foam was used as the substrate (the specific pretreatment process was as follows: the nickel foam was immersed in 0.1M hydrochloric acid, ethanol, and deionized water, respectively, and ultrasonically treated for 20 minutes each, then vacuum dried for later use). The reactor was placed in a constant temperature device and subjected to a hydrothermal reaction at an appropriate temperature for several hours. After the reaction, the electrode surface was cleaned with deionized water and ethanol to obtain the desired precursor electrode material. Subsequently, the electrode was placed in a vacuum drying oven and dried at a constant temperature. After multiple cleanings, a nickel-iron-based porous carbon heterostructure catalytic electrode was obtained.
[0024] The OER linear sweep voltammetric curve in alkaline simulated seawater is as follows: Figure 2 As shown in a, the heterostructure catalytic electrode operates at 500 mA / cm². 2 The overpotentials were 360 mV, significantly better than commercially available nickel foam. The stability curves of the OER in alkaline simulated seawater are shown below. Figure 2 As shown in b, the heterostructure catalytic electrode operates at 1 A / cm 2 It remained stable after running for 200 hours, with no significant performance degradation.
[0025] In summary, this invention proposes a method for preparing a heterogeneous catalytic anode for seawater electrolysis resistant to chlorine corrosion. This method involves modifying the surface of a nickel-iron-based electrolytic sheet structure with organic molecules to construct a nickel-iron nanosheet array catalyst with a porous carbon heterostructure. The nanosheet structure and porous carbon facilitate rapid diffusion of oxygen and electrolyte, increasing the exposure of active sites and improving catalytic efficiency. The amino-containing porous carbon on the surface forms a stable adsorption layer with the metal surface, blocking direct contact between chloride ions and the metal surface, and significantly inhibiting chlorine corrosion. Therefore, the nickel-iron nanosheet array catalyst with a porous carbon heterostructure not only exhibits excellent electrocatalytic efficiency but also significantly enhanced resistance to chlorine corrosion.
[0026] The above descriptions are merely embodiments of the present invention, and common knowledge regarding specific technical solutions or characteristics is not elaborated upon here. It should be noted that those skilled in the art can make various modifications and improvements without departing from the technical solutions of the present invention, and these should also be considered within the scope of protection of the present invention. These modifications and improvements will not affect the effectiveness of the implementation of the present invention or the practicality of the patent. The scope of protection claimed in this application should be determined by the content of its claims, and the specific embodiments described in the specification can be used to interpret the content of the claims.
Claims
1. A method for preparing a heterogeneous catalytic anode resistant to chlorine corrosion in seawater electrolysis, characterized in that: Nickel-iron nanosheet structures were constructed in situ on the surface of metal foam using a hydrothermal method, and their surfaces were then modified with organic molecules to obtain a nickel-iron nanosheet array catalyst with porous carbon coating. The alkaline simulated seawater electrolyzer constructed using this invention as the anode can achieve stable operation over a long period. The specific preparation steps are as follows: Step 1, metal foam cleaning treatment: The metal foam was cut into appropriate sizes and immersed in hydrochloric acid aqueous solution, anhydrous ethanol, and deionized water for ultrasonic treatment, and then dried for later use; Step 2, preparation of nickel-iron-based metal-organic framework precursor: Nickel salt and iron salt were weighed and dissolved in a solvent to form solution A; The organic ligand is dissolved in a solvent to form solution B; solution A and solution B are stirred and mixed evenly at 60°C to form solution C; the metal foam and solution C are placed in a hydrothermal reactor for hydrothermal reaction to obtain a nickel-iron-based metal-organic framework precursor; step three, synthesis of nickel-iron-based porous carbon heterostructure electrode: the nickel-iron-based metal-organic framework precursor is washed and dried to obtain a nickel-iron-based porous carbon heterostructure electrode.
2. The method for preparing the heterogeneous catalytic anode for chlorine corrosion resistance in seawater electrolysis according to claim 1, characterized in that, The solvent in solution A is one or both of deionized water and formamide, wherein the volume ratio of deionized water to formamide is 1:10 to 10:
1.
3. The method for preparing the chlorine-resistant heterogeneous catalytic anode for seawater electrolysis according to claim 1, characterized in that, The solvent in solution B is one or more of deionized water, methanol, and ethanol.
4. The method for preparing the chlorine-resistant heterogeneous catalytic anode for seawater electrolysis according to claim 1, characterized in that, The organic ligand in solution B is an organic amine.
5. The method for preparing the chlorine-resistant heterogeneous catalytic anode for seawater electrolysis according to claim 1, characterized in that, The molar ratio of nickel salt to iron salt is 1:10 to 10:1; the total molar concentration of metal salt in solution A is 10 to 100 mM; and the molar ratio of organic ligand to total metal salt is 5:1 to 1:
5.
6. The method for preparing the heterogeneous catalytic anode for chlorine corrosion resistance in seawater electrolysis according to claim 1, characterized in that, The metal foam includes: aluminum foam, nickel foam, and titanium foam.
7. The method for preparing the heterogeneous catalytic anode for chlorine corrosion resistance in seawater electrolysis according to claim 1, characterized in that, The hydrothermal reaction temperature is 100–200℃, and the reaction time is 10–60 h.
8. The method for preparing the chlorine-resistant heterogeneous catalytic anode for seawater electrolysis according to claim 1, characterized in that, The electrocatalyst channel contains an amino group that inhibits Cl. - It exhibits excellent selectivity for oxygen evolution reaction in alkaline simulated seawater electrolysis.