Cobalt-based metal organic framework material resistant to electrochemical reconstruction and preparation method and application of cobalt-based metal organic framework material

Abstract

The invention provides an electrochemical reconstruction resistant cobalt-based metal organic framework material as well as a preparation method and application thereof. The cobalt-based metal organic framework material is formed by coordination of trivalent cobalt and an organic ligand. The cobalt-based metal organic framework material has remarkably low overpotential, excellent reaction kinetics and a more stable crystal structure in water electrolysis oxygen evolution reaction, and a new thought is provided for application of an efficient and stable metal organic framework in water electrolysis.

Description

Technical Field

[0001] This invention relates to the field of metal-organic framework materials technology, and in particular to a cobalt-based metal-organic framework material resistant to electrochemical reconstruction, its preparation method, and its application. Background Technology

[0002] Cobalt-based metal-organic frameworks (MOFs) have great potential applications in electrocatalysis (oxygen evolution reaction and hydrogen evolution reaction) (Adv. Mater. 2022, 34(11): 2107072; Coord. Chem. Rev. 2025, 523(2): 216296). However, cobalt-based MOFs undergo surface or complete reconstruction in strong alkaline electrolytes and high-potential electrochemical oxidation, leading to crystal transformation and structural collapse, which significantly inhibits their inheritance of the advantages of high specific surface area and rich pore structure of MOFs. For example, Co atoms in MOFs will be converted to Co-OH (α / β-Co(OH)2) in alkaline oxygen evolution reaction, and further converted to Co-OOH (CoOOH) (Adv. Mater. 2021, 33(32): 2007344; Renewables 2024, 2: 272-296). Numerous in-situ experiments have demonstrated that cobalt-based metal-organic frameworks transform into α / β-Co(OH)2 during high-potential electrochemical oxidation, ultimately forming either the active phase CoOOH or the inactive phase CoO (ACS Catal. 2020, 10(1): 81-92; Nano Lett. 2025, 25(29): 11484-11491). Currently, research on cobalt-based metal-organic frameworks resistant to electrochemical reconstruction remains lacking in this field, leading to performance and stability bottlenecks in their application as water electrolysis catalysts. Summary of the Invention

[0003] In view of this, the present invention proposes a cobalt-based metal-organic framework material resistant to electrochemical reconstruction, its preparation method and application, wherein the cobalt-based metal-organic framework material can act as an active center in the electrocatalytic process without undergoing reconstruction.

[0004] The technical solution of the present invention is implemented as follows: In a first aspect, the present invention provides a cobalt-based metal-organic framework material resistant to electrochemical reconstruction, wherein the cobalt-based metal-organic framework material is formed by coordination of trivalent cobalt and organic ligands.

[0005] Specifically, this invention directly uses Co 3+ As the main metal nodes for assembling metal-organic frameworks, their electrochemical reconstruction is completely suppressed, enabling cobalt-based metal-organic frameworks to directly serve as active centers and achieve efficient and stable electrocatalytic reactions.

[0006] Specifically, the crystal structure of the cobalt-based metal-organic framework material is consistent with the crystal structure formed by divalent cobalt / zinc with the same ligand, and the crystal structure formed by divalent cobalt / zinc is ZIF-67 (Co 2+ (2-Methylimidazole)2), MAF-32 (Zn) 2+ (2-Ethylimidazole)2) and ZIF-ana (Zn 2+ One or more of (2-propylimidazolium)2). Compared to isomorphic metal-organic frameworks formed by divalent cobalt / zinc, the cobalt-based metal-organic framework of the present invention, after X-ray photoelectron spectroscopy detection, shows that some / all of the cobalt metal is in a trivalent state.

[0007] Based on the above technical solutions, preferably, the salt precursor of the trivalent cobalt is cobalt(III) acetylacetonate.

[0008] Based on the above technical solutions, preferably, the organic ligand is one or more of 2-methylimidazole, 2-ethylimidazole and 2-propylimidazole.

[0009] In a second aspect, the present invention provides a method for preparing a cobalt-based metal-organic framework material resistant to electrochemical reconstruction, comprising the following steps: S1, Cobalt(III) acetylacetone and organic ligands were mixed and ground into powder under a xenon lamp to obtain the precursor; S2, the precursor is heated in a vacuum under an inert atmosphere to obtain a cobalt-based metal-organic framework material.

[0010] Based on the above technical solutions, preferably, the molar ratio of cobalt acetylacetone (III) and organic ligand in step S1 is 1:3 to 1:8.

[0011] Based on the above technical solutions, preferably, the inert gas in step S2 is one of nitrogen, carbon dioxide, helium, neon, argon and krypton, and the gas flow rate is 100 ~ 300 cc / min.

[0012] Based on the above technical solutions, preferably, in step S2, when vacuum heating, the vacuum degree is <0.05 Pa, the temperature is raised to 140-350℃ at a heating rate of 1~10℃ / min, and held for 1~2 h.

[0013] Based on the above technical solutions, preferably, the heating temperature corresponds to the following organic ligands: 2-methylimidazole 260 ℃, 2-ethylimidazole 260 ℃, and 2-propylimidazole 140 ℃.

[0014] Thirdly, the present invention provides an application of a cobalt-based metal-organic framework material resistant to electrochemical reconstruction in electrocatalytic reactions.

[0015] Based on the above technical solutions, preferably, the electrocatalytic reaction includes one of the hydrogen evolution reaction and the oxygen evolution reaction.

[0016] Based on the above technical solutions, preferably, the conditions for the electrocatalytic reaction are: electrolyte pH > 10, oxygen evolution reaction test voltage of 0.9 ~ 1.7 V, hydrogen evolution reaction test voltage of -0.7 ~ 0 V, and scan rate of 50 V / s.

[0017] It is expected that high-valence metal ions (Fe) in this field will... 3+ Ni 3+ Mn 3+ There are numerous cobalt-based metal-organic frameworks (MOFs) and organic ligands (azoles, carboxylic acids, pyridines), and this technology can be used to prepare mixed ions and mixed ligands for electrochemical reconstruction.

[0018] The cobalt-based metal-organic framework material resistant to electrochemical reconstruction, its preparation method, and its application, as described in this invention, have the following advantages over existing technologies: (1) The cobalt-based metal-organic framework provided by this invention will not undergo complete or surface reconstruction under strongly alkaline environments and high-potential electrochemical oxidation conditions (see Figure 1 Compared to divalent cobalt / zinc isomorphic metal-organic frameworks, the cobalt-based metal-organic framework provided by this invention exhibits significantly lower overpotential, superior reaction kinetics, and a more stable crystal structure in the electrocatalytic oxygen evolution reaction. Furthermore, the cobalt-based metal-organic framework provided by this invention also demonstrates superior electrocatalytic performance compared to divalent cobalt / zinc isomorphic metal-organic frameworks in electrolytes under different pH conditions (see...). Figure 4-7 ).

[0019] (2) The method for preparing cobalt-based metal-organic frameworks provided by the present invention can effectively realize the formation of cobalt-based metal-organic frameworks. The cobalt-based metal-organic frameworks have the same structure as the isomorphic metal-organic frameworks of divalent cobalt / zinc, and have similar specific surface area, pore size distribution, and crystal morphology (see Figure 8-10 ).

[0020] (3) The electrocatalytic application testing method used in this invention only involves hot-pressing the cobalt-based metal-organic framework onto carbon paper (CP) for testing. It is expected that the electrocatalytic performance of the cobalt-based metal-organic framework can be further enhanced through doping, hybridization, and composite technologies, and it has a great potential for modification.

[0021] (4) In the early stage of preparation of cobalt-based metal-organic frameworks, this invention uses physical research The grinding process thoroughly mixes the particles to form a large number of seed crystals. The further growth process is then completed with the assistance of a thermal field. By controlling the holding time during the molten salt preparation process, the particle size of the cobalt-based metal-organic framework can be effectively controlled, making the particle size of the product powder adjustable in the range of nanometers to micrometers.

[0022] (5) The cobalt-based metal-organic framework prepared by this invention has high-temperature thermal stability, maintaining structural stability at 200–500°C, and can be stably stored for a long time under different synthesis pH ranges and air conditions (see Figure 6 Furthermore, the cobalt-based metal-organic framework prepared in this invention can also stably carry out catalytic water electrolysis reactions in electrolytes under different pH conditions. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the 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.

[0024] Figure 1 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ X-ray diffraction patterns of ZIF-67, standard ZIF-67, and standard configuration; Figure 2 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ X-ray photoelectron spectra of ZIF-67 and ZIF-67 Figure 3 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ - X-ray diffraction patterns of ZIF-67 and ZIF-67 after electrocatalytic reaction; Figure 4 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ -Polarization curves of ZIF-67 and ZIF-67 and commercial RuO2 electrocatalytic oxygen evolution reaction; Figure 5 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ Tafel slope plot of the electrocatalytic oxygen evolution reaction of ZIF-67 with ZIF-67 and commercial RuO2; Figure 6 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ - Polarization curves of oxygen evolution reaction of ZIF-67 and ZIF-67 in different pH ranges; Figure 7 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ -Polarization curves of ZIF-67 and the ZIF-67 electrocatalytic hydrogen evolution reaction: Figure 8 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ - Scanning electron microscope image of ZIF-67; Figure 9 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ -N2 isothermal adsorption-desorption curves of ZIF-67 and ZIF-67; Figure 10 The cobalt-based metal-organic framework material Co prepared in Example 1 3+ - Aperture distribution diagram of ZIF-67 and ZIF-67; Figure 11 The cobalt-based metal-organic framework material Co prepared in Example 3 3+ X-ray diffraction patterns of ZIF-ana and standard ZIF-ana; Figure 12 The cobalt-based metal-organic framework material (Co) of trivalent mixed metals prepared in Example 4 3+ Fe 3+ X-ray diffraction patterns of ZIF-67 and standard ZIF-67. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] To enable those skilled in the art to better understand the technical solution of this application, the technical solution of this application will be described in detail below with reference to specific embodiments. Unless otherwise specified, experimental conditions are generally applied according to conventional conditions or the conditions recommended by the reagent company. The reagents, consumables, etc., used in the following embodiments can be obtained commercially unless otherwise specified.

[0027] The ZIF-67 (Co) used in this invention 2+ (2-Methylimidazole)2), MAF-32 (Zn) 2+ (2-Ethylimidazole)2), ZIF-ana (Zn) 2+ (2-Propylimidazol)2) The standard XRD patterns were obtained by exporting the crystal CIF files from the Cambridge Crystal Database (CCDC) and importing them into Materials Studio software for simulation.

[0028] Example 1

[0029] This embodiment provides a cobalt-based metal-organic framework material Co that is resistant to electrochemical reconstruction. 3+ The preparation method of ZIF-67 specifically includes the following steps: S1. 3.563 g of cobalt(III) acetylacetonate (10 mmol) and 3.284 g of 2-methylimidazole (40 mmol) were placed in a mortar and physically ground into a fine powder with uniform color (particle size 20 ~ 100 μm) at a molar ratio of 1:4 to obtain the precursor.

[0030] S2. The precursor obtained in step S1 is evenly spread in a quartz crucible, and then the quartz crucible is placed in a tube furnace. A protective atmosphere is introduced for heating treatment. The specific process conditions are: vacuum degree < 0.05 Pa, heating to 100 ℃ at a heating rate of 3 ℃ / min at room temperature, then heating to 260 ℃ at a heating rate of 5 ℃ / min, and holding at this temperature for 1.5 h. The protective atmosphere is argon, and the gas flow rate is 100 cc / min. After heating, the furnace is cooled to room temperature to obtain Co. 3+ -ZIF-67 material.

[0031] Comparative Example 1 Take ZIF-67 (Co 2+ (2-Methylimidazole)2) is Comparative Example 1, in which cobalt acetylacetonate (II) is used instead of cobalt acetylacetonate (III), and the other contents are the same as in Example 1.

[0032] The Co prepared in this embodiment was tested and found to be effective. 3+ The yield of ZIF-67 is around 90%, and it remains thermally stable in water or other solvents within a temperature range of 100–600 °C.

[0033] Figure 1 The Co prepared in Example 1 of this study 3+ X-ray diffraction patterns of ZIF-67, ZIF-67 of Comparative Example 1, and standard ZIF-67 indicate that Co 3+ -ZIF-67 has the same configuration as standard ZIF-67, and indicates that Co 3+ -ZIF-67 contains no impurities and has a purity of over 95%.

[0034] Figure 2 The Co prepared in Example 1 of this study 3+ X-ray photoelectron spectra of ZIF-67 and ZIF-67 prepared in Comparative Example 1 show that the prepared Co 3+ In ZIF-67, the Co metal is a mixture of trivalent and divalent, with trivalent Co accounting for 42.2%. In contrast, the Co metal in ZIF-67 prepared in Comparative Example 1 is all divalent.

[0035] Combination Figure 1 and Figure 2 This fully demonstrates Co 3+ The successful preparation of ZIF-67 and its trivalent properties of Co metal.

[0036] Figure 3 The Co prepared in Example 1 of this study 3+ X-ray diffraction patterns of ZIF-67 material and ZIF-67 material prepared in Comparative Example 1, loaded on carbon paper and subjected to electrocatalytic oxygen evolution reaction in a 1 M KOH electrolyte, show that after the catalytic reaction, the ZIF-67 material prepared in Comparative Example 1 formed obvious CoOOH crystal peaks, indicating a reconstruction phenomenon, while Co... 3+ -ZIF-67 retains its original configuration, fully demonstrating the high stability of the metal-organic framework formed by trivalent cobalt in electrochemical environments.

[0037] Figure 4 The Co prepared in Example 1 of this study 3+ The polarization curves of the electrocatalytic oxygen evolution reaction (OER) of ZIF-67 material and Comparative Example 1 prepared with commercial RuO2 (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) were measured in a 1 M KOH electrolyte using a standard three-electrode setup under the same conditions. (The data were obtained at 10 mA / cm².) 2 At current density, Co 3+ -ZIF-67 has an overpotential of only 249 mV, which is better than ZIF-67 prepared in Comparative Example 1 and commercial RuO2 (both of which are 311 mV).

[0038] Figure 5 The Co prepared in Example 1 of this study 3+ Tafel slope plots of the electrocatalytic oxygen evolution reaction (OER) using ZIF-67 material, ZIF-67 material prepared in Comparative Example 1, and commercial RuO2 (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) in a 1 M KOH electrolyte. (The data is presented at 10 mA / cm².) 2 At current density, Co 3+ -ZIF-67 material has a voltage of only 116 mV·dec -1 The value was lower than that of the ZIF-67 material prepared in Comparative Example 1 (121 mV·dec). -1 ) and commercial RuO2 materials (137 mV·dec) -1 ).

[0039] Figure 6 Co prepared in this embodiment 3+The polarization curves of the ZIF-67 material and the ZIF-67 material prepared in Comparative Example 1 under different pH conditions illustrate the effects of Co on the electrocatalytic oxygen evolution reaction. 3+ -ZIF-67 outperforms divalent isomorphic metal-organic frameworks in the 12.5~14 range and exhibits better reactivity in alkaline electrolytes.

[0040] Figure 7 Co prepared in this embodiment 3+ The polarization curves of the electrocatalytic hydrogen evolution reaction of ZIF-67 material and the ZIF-67 material prepared in Comparative Example 1 were measured in a 1 M KOH electrolyte using a standard three-electrode setup under the same conditions. It is evident that Co... 3+ -ZIF-67 exhibits superior hydrogen evolution reaction performance compared to ZIF-67. Tests have shown that the material does not undergo remodeling after the hydrogen evolution reaction.

[0041] Combination Figures 3-7 This fully demonstrates the superiority of the metal-organic framework formed by trivalent cobalt in terms of comprehensive electrocatalytic performance.

[0042] Example 2

[0043] This embodiment provides a cobalt-based metal-organic framework material Co that is resistant to electrochemical reconstruction. 3+ The preparation method of MAF-32 specifically includes the following steps: S1. Mix 3.563 g of cobalt(III) acetylacetonate (10 mmol) and 2.884 g of 2-ethylimidazole (30 mmol) (molar ratio 1:3), and physically grind them in a mortar into a fine powder with uniform color (particle size 20 ~ 100 μm) to obtain the precursor. S2. The precursor obtained in step S1 is evenly spread in a quartz crucible, and then the quartz crucible is placed in a tube furnace. A protective atmosphere is introduced for heating treatment. The specific process conditions are: vacuum degree < 0.05 Pa, room temperature, direct heating to 260 ℃ at a heating rate of 5 ℃ / min, holding at 1 h, the protective atmosphere is argon, and the gas flow rate is 100 cc / min. After heating, the furnace is cooled to room temperature to obtain Co. 3+ -MAF-32 material.

[0044] The Co prepared in this embodiment was tested and found to be effective. 3+ The yield of -MAF-32 is approximately 70%, and it remains thermally stable in water or other solvents within a temperature range of 100–500 °C. Electrochemical tests show that Co... 3+ -MAF-32 exhibits superior electrochemical catalytic performance in the oxygen evolution reaction compared to MAF-32 constructed from divalent cobalt, and the X-ray diffraction pattern after the reaction does not show the characteristic peak of CoOOH.

[0045] Example 3

[0046] This embodiment provides a cobalt-based metal-organic framework material Co that is resistant to electrochemical reconstruction. 3+ The preparation method of ZIF-ana material specifically includes the following steps: S1. Mix 3.563 g of cobalt(III) acetylacetonate (10 mmol) and 6.610 g of 2-propylimidazole (60 mmol) (molar ratio 1:6), and physically grind them in a mortar into a fine powder with uniform color (particle size 20 ~ 100 μm) to obtain the precursor. S2. The precursor obtained in step S1 is evenly spread in a quartz crucible, which is then placed in a tube furnace and heated under a protective atmosphere. The specific process conditions are as follows: the temperature is directly increased to 140 ℃ at a heating rate of 1 ℃ / min at room temperature, and held for 1 h. The protective atmosphere is argon with a gas flow rate of 200 cc / min. After heating, the furnace is cooled to room temperature to obtain Co. 3+ -ZIF-ana material.

[0047] The Co prepared in this embodiment was tested and found to be effective. 3+ The yield of -ZIF-ana is about 80%, and it remains thermally stable in water or other solvents within a temperature range of 100 to 500 °C.

[0048] Figure 11 The Co prepared in this embodiment 3+ -ZIF-ana and Standard ZIF-ana (Zn 2+ The X-ray diffraction pattern of (2-propylimidazolium)2 indicates that Co 3+ -ZIF-ana is consistent with the standard lattice and indicates that Co 3+ -ZIF-ana is free of impurities, with a purity of over 95%. Electrochemical tests show that Co... 3+ -ZIF-ana exhibits superior performance in electrochemical catalysis of oxygen evolution reaction compared to ZIF-ana constructed from divalent cobalt, and the X-ray diffraction pattern after the reaction does not show the characteristic peak of CoOOH.

[0049] Example 4

[0050] This embodiment provides a highly stable Co 3+ Fe 3+ The preparation method of ZIF-67 material, in this embodiment, introduces multiple high-valence metals and specifically includes the following steps: S1. Mix 3.563 g of cobalt(III) acetylacetone and 1.514 g of iron(III) acetylacetone (molar ratio 7:3), add 7.037 g of 2-methylimidazole and mix well (molar ratio of total metal to 2-methylimidazole 1:6), place in a mortar and physically grind into a fine powder with uniform color (particle size 20 ~ 100 μm) to obtain the precursor; S2. The precursor obtained in step S1 is evenly spread in a quartz crucible, and then the quartz crucible is placed in a tube furnace. A protective atmosphere is introduced for heating treatment. The specific process conditions are: vacuum degree < 0.05 Pa, room temperature, heating directly to 260 ℃ at a heating rate of 5 ℃ / min, holding at this temperature for 2 h, the protective atmosphere is argon, and the gas flow rate is 200 cc / min. After heating, the furnace is cooled to room temperature to obtain Co. 3+ Fe 3+ -ZIF-67 material.

[0051] The Co prepared in this embodiment was tested and found to be effective. 3+ Fe 3+ The yield of ZIF-67 is about 80%, and it remains thermally stable in water or other solvents within a temperature range of 100–500°C.

[0052] Figure 12 The Co prepared in this embodiment 3+ Fe 3+ X-ray diffraction patterns of ZIF-67 and standard ZIF-67 indicate that Co 3+ Fe 3+ -ZIF-67 is consistent with the standard lattice and indicates that Co 3+ Fe 3+ -ZIF-67 is free of impurities, with a purity exceeding 95%. Electrochemical testing shows that Co... 3+ Fe 3+ -ZIF-67 exhibits superior performance in electrochemical catalysis of oxygen evolution reaction compared to ZIF-67 constructed from divalent cobalt, and the X-ray diffraction pattern after the reaction does not show the characteristic peak of CoOOH.

[0053] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the molar ratio of cobalt acetylacetonate (III) to 2-methylimidazole is 1:2, specifically: 3.563 g cobalt acetylacetonate (III) (10 mmol) and 1.642 g 2-methylimidazole (20 mmol). The rest is the same as in Example 1.

[0054] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the molar ratio of cobalt acetylacetonate (III) to 2-methylimidazole is 1:9, specifically: 3.563 g cobalt acetylacetonate (III) (10 mmol) and 7.389 g 2-methylimidazole (90 mmol). The rest is the same as in Example 1.

[0055] Testing revealed that Comparative Examples 2 and 3 could not produce X-ray diffraction patterns consistent with the standard ZIF-67, indicating the inapplicability of these two proportions.

[0056] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A cobalt-based metal-organic framework material resistant to electrochemical reconstruction, characterized in that: The cobalt-based metal-organic framework material is formed by coordination of trivalent cobalt and organic ligands.

2. The cobalt-based metal-organic framework material resistant to electrochemical reconstruction as described in claim 1, characterized in that: The salt precursor of the trivalent cobalt is cobalt(III) acetylacetonate.

3. The cobalt-based metal-organic framework material resistant to electrochemical reconstruction as described in claim 2, characterized in that: The organic ligand is one or more of 2-methylimidazole, 2-ethylimidazole and 2-propylimidazole.

4. The method for preparing a cobalt-based metal-organic framework material resistant to electrochemical reconstruction as described in claim 3, characterized in that: Includes the following steps: S1, Cobalt(III) acetylacetone and organic ligands were mixed and ground into powder under a xenon lamp to obtain the precursor; S2, the precursor is heated in a vacuum under an inert atmosphere to obtain a cobalt-based metal-organic framework material.

5. The method for preparing a cobalt-based metal-organic framework material resistant to electrochemical reconstruction as described in claim 4, characterized in that: The molar ratio of cobalt(III) acetylacetone to the organic ligand in step S1 is 1:3 to 1:

8.

6. The method for preparing a cobalt-based metal-organic framework material resistant to electrochemical reconstruction as described in claim 4, characterized in that: During vacuum heating in step S2, the vacuum degree is <0.05 Pa, and the temperature is increased to 140-350℃ at a heating rate of 1~10 ℃ / min, and held for 1~2 h.

7. The application of a cobalt-based metal-organic framework material resistant to electrochemical reconstruction as described in any one of claims 1-3 in electrocatalytic reactions.

8. The application as described in claim 7, characterized in that: The electrocatalytic reaction includes one of the hydrogen evolution reaction and the oxygen evolution reaction.

9. The application as described in claim 8, characterized in that: The conditions for the electrocatalytic reaction are: electrolyte pH > 10, oxygen evolution reaction test voltage of 0.9 ~ 1.7 V, hydrogen evolution reaction test voltage of -0.7 ~ 0 V, and scan rate of 50 V / s.

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