Long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of electrocatalyst material preparation, and discloses a long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst as well as a preparation method and application thereof, fluorine-doped cobalt selenide nanobelts prepared by a low-temperature annealing method are used as a base material, and the CoOOH ultrathin nanosheet electrocatalyst is prepared by in-situ reconstruction under an alkaline electrolyzed water anode oxygen evolution reaction condition. In the preparation process of the CoOOH ultrathin nanosheet provided by the invention, lattice cobalt is stabilized in the water electrolysis anode reconstruction process through fluorine ions with strong bonding action with cobalt ions, so that the long-range disordered structure of amorphous CoOOH generated after reconstruction is limited by localization, and the alkaline water electrolysis anode reaction performance is improved. The catalyst has activity and durability obviously superior to those of a commercial ruthenium oxide catalyst in industrial application of anion exchange membrane water electrolysis hydrogen production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electrocatalyst material preparation, and particularly relates to a long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst and a preparation method and application thereof. BACKGROUND

[0002] To cope with the development goals of carbon peak and carbon neutral, the energy structure is in urgent need of transformation from traditional fossil fuels with high carbon emissions to new renewable energy with low carbon. As a clean and sustainable energy, the hydrogen energy industry has ushered in an unprecedented development opportunity. As one of the key technologies for green hydrogen production, alkaline anion exchange membrane water electrolysis for hydrogen production has become a low-cost and high-efficiency hydrogen production process that has attracted much attention because it can use non-noble metal catalysts. However, the sluggish reaction kinetics of anode oxygen evolution greatly limits the large-scale development of alkaline anion exchange membrane water electrolysis for hydrogen production. Therefore, it is extremely important to develop low-cost and high-efficiency non-noble metal catalysts to realize the large-scale development of alkaline anion exchange membrane water electrolysis for hydrogen production.

[0003] Currently, cobalt oxyhydroxide (CoOOH) has a moderate degradation rate and adjustable activity, and is outstanding in transition metal non-oxide water electrolysis anode catalysts, and is considered to be one of the most promising alkaline water electrolysis hydrogen production anode catalysts. At the same time, long-range disordered amorphous nanostructures have the outstanding characteristics of exposing many reaction sites and being corrosion-resistant, and these amorphous catalysts can effectively realize the adsorption regulation of reaction intermediates by adjusting the long-range disorder degree, thereby accelerating the catalytic reaction kinetics. For example, Angewandte Chemie International Edition 64, e202421263, 2025 reported that the increase in the structural long-range order of poly- (heptazine imide) nanorods can greatly enhance the separation of photo-generated charges and the adsorption of CO intermediates in the photocatalytic CO2 methanation, thereby improving the catalytic performance. Therefore, designing and constructing amorphous CoOOH nanostructure catalysts with different long-range disorder degrees is of great significance for realizing efficient alkaline water electrolysis for hydrogen production.

[0004] However, under the anode reaction conditions of alkaline water electrolysis, cobalt-based catalysts will inevitably undergo oxidation reconstruction, resulting in the failure of the structural design of the initial catalyst and the lack of control over the structure of the amorphous CoOOH catalyst formed after reconstruction, ultimately leading to poor efficiency and stability of the water electrolysis for hydrogen production. So far, in the development of alkaline water electrolysis anode catalyst materials, research on controlling the long-range disorder degree of amorphous CoOOH catalysts formed after reconstruction is still rare, making the current alkaline water electrolysis hydrogen production anode catalyst still unable to effectively benefit from the long-range disorder degree control of the reconstructed amorphous CoOOH structure to achieve a significant performance improvement.

[0005] In summary, there is still a lack of a technology that can dynamically control the long-range disorder degree of the amorphous CoOOH catalyst formed by reconstruction in the process of water electrolysis anodic oxidation, so that the amorphous CoOOH catalyst material cannot exhibit its theoretically unique high activity and high stability in the actual water electrolysis hydrogen production process. Therefore, it is urgent to develop a necessary long-range disorder degree regulation process for the amorphous CoOOH formed by reconstruction under the condition of water electrolysis anodic oxidation, so as to develop a kind of alkaline water electrolysis hydrogen production catalyst material with high performance and high stability. SUMMARY

[0006] In order to overcome the above-mentioned shortcomings of the prior art, the purpose of the present application is to provide a long-range disorder localized CoOOH ultrathin nanosheet electrocatalyst and its preparation method and application, so as to solve the problem that the long-range disorder of the active phase of the amorphous hydroxide oxide formed by oxidation and reconstruction in the process of the existing water electrolysis hydrogen production anode catalyst technology is difficult to control and cannot meet the reaction efficiency and durability requirements in the process of alkaline water electrolysis.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: The first purpose of the present application is to provide a long-range disorder localized CoOOH ultrathin nanosheet electrocatalyst, which has a limited long-range disorder amorphous structure and realizes high-performance and high-stability industrialized water electrolysis hydrogen production application.

[0008] The long-range disorder localized CoOOH ultrathin nanosheet has an ordered-disordered crystal structure interface, and there is a tensile stress at the interface, which promotes the activation and regeneration of lattice oxygen in the process of water electrolysis anode oxygen evolution reaction.

[0009] The second purpose of the present application is to disclose a preparation method of the long-range disorder localized CoOOH ultrathin nanosheet electrocatalyst: fluorine-doped cobalt selenide nanobelt is prepared as a basic material by a low-temperature annealing method, and is prepared in situ under the condition of alkaline water electrolysis anode oxygen evolution reaction.

[0010] More specifically, first, the fluorine salt and the CoSe2 nanobelt are obtained by a low-temperature annealing method to obtain F-CoSe2 nanobelt, and then the prepared F-CoSe2 nanobelt is prepared in situ under the condition of alkaline water electrolysis anode oxidation reaction (the element F is dissolved in the solution in the process of electrochemical oxidation) to prepare long-range disorder localized CoOOH ultrathin nanosheet, i.e. electrocatalyst.

[0011] As a preferred scheme, the in-situ reconstruction process adopts a cyclic voltammetry method, and the specific operation is as follows: The F-CoSe2 nanobelt is dispersed in a mixed solution of isopropyl alcohol and Nafion to form a dispersion slurry; The dispersed slurry is coated on the surface of the gas diffusion layer, and after drying, a working electrode is formed; In the oxygen-saturated potassium hydroxide electrolyte, cyclic voltammetry is performed to complete in-situ reconstruction.

[0012] Further, the mass fraction of the Nafion solution is 5%, and the concentration of the potassium hydroxide electrolyte is 1 mol / L.

[0013] Further, the cyclic voltammetry condition is that the voltage range is 1.02-1.50 V, the scanning rate is 50 mV / s, and the cyclic treatment is 30-50 times to complete in-situ reconstruction.

[0014] As a preferred scheme, the anodic oxidation of electrolytic water can also adopt a constant voltage test method.

[0015] As a preferred scheme, the preparation of the F-CoSe2 nanobelt specifically includes the following steps: Step 1, mixing polyethylene polyamine, water, cobalt salt and selenate and fully stirring to prepare a dispersed solution, and then centrifuging, washing and drying after heating reaction to prepare CoSe2 nanobelt; Step 2, annealing the prepared CoSe2 nanobelt with a fluorine salt at a certain temperature, and then centrifuging, washing and drying after reaction to prepare F-CoSe2 nanobelt.

[0016] As a preferred scheme, the cobalt salt is one of cobalt sulfate, cobalt chloride, cobalt acetate, cobalt acetylacetone and cobalt nitrate; preferably, the selenate is one of sodium selenite and potassium selenite; preferably, the polyethylene polyamine is a mixture of one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0017] As a preferred scheme, the molar ratio of the cobalt salt to the selenate is (1-3):(1-4), and the volume ratio of the polyethylene polyamine to water in the aqueous solution of the polyethylene polyamine is (2-5):(1-2).

[0018] As a preferred scheme, the fluorine salt is one of sodium fluoride, ammonium fluoride and potassium fluoride.

[0019] As a preferred scheme, the molar ratio of the CoSe2 nanobelt to the fluorine salt is 1:(1-45).

[0020] A third object of the present application is the application of the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst in the anodic oxygen evolution reaction of alkaline electrolytic water and the industrial anion exchange membrane electrolytic water hydrogen production.

[0021] Compared with the prior art, the present application has the following beneficial effects: The long-range disorder localized CoOOH ultrathin nanosheet electrocatalyst disclosed by the application is a low crystal structure prepared by reconstruction of F-CoSe2 nanobelt under the anode reaction condition of alkaline electrolytic water, wherein the replacement of F ions to Se ions in the base material can reduce the leaching of lattice Co atoms, and can also adjust the electronic structure of Co sites, so that the long-range disorder degree of the amorphous CoOOH after reconstruction is effectively controlled, thereby obtaining the long-range disorder localized amorphous CoOOH ultrathin nanosheet. At the same time, due to the participation of fluorine ions, when applied to the anode oxygen evolution reaction of alkaline electrolytic water, the lattice Co is easy to remain during the reconstruction process, and a limited long-range disorder structure is constructed, so it has excellent catalytic activity and durability in the anode oxygen evolution reaction of alkaline electrolytic water, and plays a unique and significant role in the industrial hydrogen production by electrolytic water, and exhibits excellent hydrogen production efficiency and durability. In particular, in the optimal embodiment provided by the application, when the current density is 10 mA / cm 2 , the overpotential of the long-range disorder localized CoOOH ultrathin nanocatalyst is only 245 mV, which is reduced by 91 mV compared with the commercial RuO2 catalyst. At the same time, under the overpotential of 295 mV, the current density of the long-range disorder localized CoOOH nanocatalyst is 30.7 times higher than that of the RuO2 catalyst, which shows excellent catalytic activity. In addition, in the industrial application of alkaline anion exchange membrane electrolytic water hydrogen production, the long-range disorder localized CoOOH ultrathin nanocatalyst realizes a current density of 3.4 A / cm 2 at 2.0 V, which is 5.4 times higher than that of the commercial RuO2 catalyst. After 1200 hours of durability test under the industrial current density of 500 mA / cm 2 , the attenuation rate of the long-range disorder localized CoOOH ultrathin nanocatalyst is only 0.09 mV / h, which reflects excellent durability of industrial electrolytic water hydrogen production. Therefore, the obtained long-range disorder localized CoOOH ultrathin nanosheet catalyst has significant application advantages in the industrial alkaline anion exchange membrane electrolytic water hydrogen production.

[0022] The preparation method of the above long-range disorder localized CoOOH ultrathin nanosheet disclosed by the application uses abundant and low-cost cobalt, selenium, fluorine and the like as raw materials, and is prepared by in-situ reconstruction under the anode reaction environment of electrolytic water. Compared with the traditional design method of electrolytic water anode catalyst, the preparation conditions are simple and mild, the cost is extremely low, the design and optimization of the real surface structure of the electrolytic water anode catalyst can be realized simply and quickly, and large-scale industrial production is easy. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 Transmission electron microscope image of the F-CoSe2 nanobelt base prepared in Example 1.

[0024] Figure 2XPS spectra of F-CoSe2 nanobelt substrate prepared in Example 1 and long-range disordered highly localized CoOOH ultrathin nanosheets formed after in-situ restructuring of water electrolysis anode. s

[0025] Figure 3 Transmission electron microscope image of long-range disordered highly localized CoOOH ultrathin nanosheets prepared in Example 1, wherein Figure 3 (a) in FIG. 1 is a low-magnification transmission electron microscope image, Figure 3 (b) in FIG. 1 is a high-resolution transmission electron microscope image.

[0026] Figure 4 X-ray diffraction spectra comparison of F-CoSe2 nanobelt substrate prepared in Example 1 and long-range disordered highly localized CoOOH ultrathin nanosheets formed after in-situ restructuring of water electrolysis anode.

[0027] Figure 5 Linear sweep curves of long-range disordered highly localized CoOOH ultrathin nanosheets prepared in Example 1 and commercial RuO2 catalyst in the process of alkaline water electrolysis anode oxygen evolution reaction.

[0028] Figure 6 Linear sweep curves of long-range disordered moderately localized CoOOH ultrathin nanosheets prepared in Example 2 and commercial RuO2 catalyst in the process of alkaline water electrolysis anode oxygen evolution reaction.

[0029] Figure 7 Linear sweep curves of long-range disordered lowly localized CoOOH ultrathin nanosheets prepared in Example 3 and commercial RuO2 catalyst in the process of alkaline water electrolysis anode oxygen evolution reaction.

[0030] Figure 8 Performance test curve of long-range disordered highly localized CoOOH ultrathin nanosheets prepared in Example 1 in the process of water electrolysis hydrogen production by anion exchange membrane.

[0031] Figure 9 Durability test curve of long-range disordered highly localized CoOOH ultrathin nanosheets prepared in Example 1 in the process of water electrolysis hydrogen production by anion exchange membrane. DETAILED DESCRIPTION

[0032] ​In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts should fall within the scope of protection of the present invention.

[0033] It should be noted that the terms "first", "second", etc. in the description and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that the numbers used in this way can be interchanged where appropriate, so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0034] The present invention is described in further detail below with reference to the accompanying drawings: Example 1 A method for preparing a long-range disordered localized CoOOH nanosheet electrocatalyst comprises the following steps: (1) Preparation of CoSe2 nanobelt substrate 1 mmol of cobalt acetate tetrahydrate and 1 mmol of sodium selenite were dissolved in a mixed solution of water and ethanol and reacted at 180°C for 16 h. The obtained sample was centrifuged, washed and dried with deionized water and ethanol to obtain a CoSe2 nanobelt substrate.

[0035] (2) Preparation of F-CoSe2 nanobelt substrate At room temperature, 1 mmol CoSe2 nanobelts and 12 mmol ammonium fluoride were placed on both sides of a quartz boat, respectively, and reacted at 200°C for 2 h. The obtained sample was centrifuged, washed, and dried with deionized water and ethanol to obtain the F-CoSe2 nanobelt substrate. Figure 1 Transmission electron microscopy image of F-CoSe2 nanobelts, demonstrating the successful preparation of the two-dimensional nanobelt substrate.

[0036] (3) Preparation of long-range disordered and highly localized CoOOH ultrathin nanosheets The F-CoSe2 nanoribbons prepared above were dispersed in a mixed solution of 1 mL isopropanol and 5% mass fraction of Nafion, and coated on the surface of a gas diffusion layer as a working electrode. In an oxygen-saturated 1 M potassium hydroxide solution, 40 cycles were performed by cyclic voltammetry at a voltage range of 1.02 to 1.50 V (vs. RHE) at a scan rate of 50 mV / s, to obtain long-range disordered highly localized CoOOH ultrathin nanosheets after reconstruction. Figure 2 F 1 of the F-CoSe2 nanoribbon substrate prepared in Example 1 and the long-range disordered highly localized CoOOH ultrathin nanosheets formed after in-situ reconstruction of the substrate in water electrolysis anode. s XPS spectrum of F-CoSe2 nanoribbons prepared in Example 1, which proves the successful introduction of F element into the selenide substrate and complete precipitation under the anode oxidation condition of water electrolysis. Example 2 The difference between this example and Example 1 is that the amount of ammonium fluoride added is different, specifically 8 mmol of ammonium fluoride is added during low-temperature annealing.

[0037] Example 3 The difference between this example and Example 1 is that the amount of ammonium fluoride added is different, specifically 4 mmol of ammonium fluoride is added during low-temperature annealing.

[0038] Structural test.

[0039] 1. Transmission electron microscopy test and elemental analysis.

[0040] Figure 1 Transmission electron microscope image of F-CoSe2 nanoribbons prepared in Example 1, the obtained sample is a ribbon structure with a width of 100-200 nm.

[0041] Figure 2 F 1 of the F-CoSe2 nanoribbon substrate prepared in Example 1 and the long-range disordered highly localized CoOOH ultrathin nanosheets formed after in-situ reconstruction of the substrate in water electrolysis anode. s XPS spectrum of F-CoSe2 nanoribbons prepared in Example 1, in which the existence of F-Co bond can be observed, confirming the introduction of F into the CoSe2 nanoribbons. Through electrochemical oxidation reconstruction, the F-Co bond disappears, indicating that F is completely leached from the CoOOH structure during the reconstruction process.

[0042] Figure 3 In (a) of FIG. 1, a transmission electron microscope image of long-range disordered highly localized CoOOH nanosheets prepared in Example 1 is shown, as shown in Figure 3 In (b) of FIG. 1, the obtained product is CoOOH ultrathin nanosheets with highly localized long-range disordered structure.

[0043] 2. X-ray diffraction spectrum.

[0044] Figure 4 X-ray diffraction spectra of F-CoSe2 nanobelt and long-range disordered highly localized CoOOH nanosheet prepared in Example 1. It can be seen from the spectra that the obtained F-CoSe2 nanobelt substrate is a cubic cobalt diselenide structure, and the long-range disordered highly localized CoOOH nanosheet obtained after reconstruction is an amorphous structure. Figure 4

[0045] Performance test.

[0046] 1. Performance test and comparative analysis of long-range disordered highly localized CoOOH nanosheet in alkaline electrolytic water anode oxygen evolution reaction.

[0047] The long-range disordered highly localized CoOOH nanocatalyst prepared in the above Example 1 was made into a working electrode and its catalytic activity in alkaline electrolytic water anode oxygen evolution reaction was measured in 1 M potassium hydroxide solution saturated with oxygen. The obtained linear scan curve is as shown in Figure 5 At a current density of 10 mA / cm 2 , the overpotential of the long-range disordered highly localized CoOOH nanocatalyst was only 245 mV, which was reduced by 91 mV compared with the commercial RuO2 catalyst. At the same time, the current density of the long-range disordered highly localized CoOOH nanocatalyst was 30.7 times higher than that of the RuO2 catalyst at a 295 mV overpotential, showing excellent electrolytic water anode oxygen evolution reaction activity.

[0048] The long-range disordered moderately localized CoOOH nanosheet prepared in the above Example 2 was treated in the same way and its catalytic performance was tested, and the obtained linear scan curve is as shown in Figure 6 At a current density of 10 mA / cm 2 , the overpotential of the long-range disordered moderately localized CoOOH nanocatalyst was only 271 mV, which was reduced by 65 mV compared with the commercial RuO2 catalyst. At the same time, the current density of the long-range disordered moderately localized CoOOH catalyst was 7.1 times higher than that of the RuO2 catalyst at a 295 mV overpotential, showing excellent electrolytic water anode oxygen evolution reaction activity.

[0049] The long-range disordered lowly localized CoOOH nanosheet prepared in the above Example 3 was treated in the same way and its catalytic performance was tested, and the obtained linear scan curve is as shown in Figure 7 At a current density of 10 mA / cm 2 ​At the same time, under the overpotential of 295 mV, the current density of the long-range disorder low-localization CoOOH nanocatalyst is 3.6 times higher than that of the RuO2 catalyst, showing excellent activity of water electrolysis anode oxygen evolution reaction.

[0050] 2. Performance test and analysis of long-range disorder localization CoOOH nanosheet in industrial anion exchange membrane water electrolysis hydrogen production.

[0051] The long-range disorder high-localization CoOOH nanocatalyst prepared in the above embodiment 1 was made into a membrane electrode and its performance in industrial anion exchange membrane water electrolysis hydrogen production was measured in 1M potassium hydroxide solution. The obtained current-voltage curve is shown in Figure 8 , which presents a current density of 3.4 A / cm 2 at 2.0 V, which is 5.4 times higher than that of the commercial RuO2 catalyst, showing excellent anion exchange membrane water electrolysis hydrogen production activity. In addition, as shown in Figure 9 , after 1200 hours of stability test at a current density of 500 mA / cm 2 , the attenuation rate of the long-range disorder high-localization CoOOH nanocatalyst is only 0.09 mV / h, which is much lower than the 2.34 mV / h of the commercial RuO2 catalyst, showing excellent durability of anion exchange membrane water electrolysis hydrogen production.

[0052] In addition, the electrocatalyst materials prepared by the present application and the existing electrocatalyst materials were also compared in terms of anion exchange membrane water electrolysis hydrogen production performance, and the results are shown in Table 1 below: Table 1

[0053] In Table 1, CoOOH-CO3 2- / SeO x 2- is a kind of ultrathin nanosheet electrocatalyst disclosed in Chinese invention patent CN118422263A, and RuO2 is also a kind of commonly used water electrolysis hydrogen production related catalyst in the art, which can improve the corrosion resistance and electrocatalytic activity of the electrode. As can be seen from the data in Table 1, the long-range disorder high-localization CoOOH nanocatalyst designed and developed by the present application is better than the traditional catalyst RuO2 and the previously disclosed CoOOH-CO3 2- / SeO x 2-The ultrathin nanosheet electrocatalyst has great advantages in the application of hydrogen production by water electrolysis in anion exchange membrane, and the current density at 2V is increased by 5.4 times and 4.2 times respectively, and the ultrathin nanosheet electrocatalyst can be stably maintained for 1200 hours under industrial current density, and has excellent performance in hydrogen production by water electrolysis in anion exchange membrane.

[0054] In conclusion, the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst provided by the application is prepared by a low-temperature annealing method, and fluorine-doped cobalt selenide nanobelt is used as a basic material and is prepared in situ under the condition of alkaline water electrolysis anode oxygen evolution reaction. In the preparation process of the CoOOH ultrathin nanosheet provided by the application, the fluorine ion with strong bonding effect with cobalt ion is used to stabilize the lattice cobalt in the water electrolysis anode reconstruction process, so that the long-range disordered structure of the amorphous CoOOH generated after reconstruction is limited by localization, thereby improving the performance of the water electrolysis anode reaction. The catalyst has significantly better activity and durability than the commercial ruthenium oxide catalyst in the industrial application of hydrogen production by water electrolysis in anion exchange membrane.

[0055] The above content only illustrates the technical idea of the application, and cannot limit the protection scope of the application. Any modification made according to the technical idea of the application on the basis of the technical scheme falls within the protection scope of the claims of the application.

Claims

1. A long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst, characterized by: The electrocatalyst is a low-crystalline structure obtained by reconstructing F-CoSe2 nanobelts under alkaline water electrolysis anode reaction conditions. Its chemical composition is CoOOH, and there is an interface of ordered-disordered crystal structure.

2. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 1, characterized in that: include: F-CoSe2 nanobelts were in situ reconstructed under alkaline water electrolysis anodic reaction conditions to produce long-range disordered localized CoOOH ultrathin nanosheet electrocatalysts.

3. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 2, characterized in that: The in-situ reconstruction treatment adopts cyclic voltammetry, and the specific operation is as follows: The F-CoSe2 nanobelts were dispersed in a mixed solution of isopropyl alcohol and Nafion to form a dispersed slurry; Applying the dispersed slurry to the surface of the gas diffusion layer and forming a working electrode after drying; In situ reconstruction was achieved by cyclic voltammetry in an oxygen-saturated potassium hydroxide electrolyte.

4. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 3, characterized in that: The mass fraction of the Nafion solution is 5%, and the concentration of the potassium hydroxide electrolyte is 1 mol / L.

5. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 3, characterized in that: The cyclic voltammetry treatment conditions are: in the voltage range of 1.02-1.50 V, at a scan rate of 50 mV / s, cycle treatment 30-50 times to complete in situ reconstruction.

6. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 2, characterized in that: The preparation of F-CoSe2 nanoribbons includes the following steps: Step 1: Polyethylene polyamine and water are mixed to prepare a solvent, and then cobalt salt and selenate are added to the solvent and stirred to prepare a polyethylene polyamine-water solution of cobalt salt-selenate, and after heating for reaction, centrifugation, washing, and drying are performed to prepare CoSe2 nanobelts; Step 2: The CoSe2 nanobelts are subjected to a substitution reaction with fluoride salt under low temperature annealing, and then washed and dried to obtain F-CoSe2 nanobelts.

7. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 6, characterized in that: The cobalt salt is cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt chloride or cobalt acetylacetonate; the selenate is sodium selenite or potassium selenite; and the polyethylene polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

8. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 6, characterized in that: The molar ratio of the cobalt salt to the selenate is (1-3): (1-4), and the volume ratio of the polyethylene polyamine to water in the aqueous solution is (2-5): (1-2).

9. The method for preparing the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 6, characterized in that: The fluoride salt is sodium fluoride, ammonium fluoride or potassium fluoride, and the molar ratio of the CoSe2 nanobelt to the fluoride salt is 1:(1-45).

10. Application of the long-range disordered localized CoOOH ultrathin nanosheet electrocatalyst according to claim 1 in the anodic oxygen evolution reaction of water electrolysis and industrial anion exchange membrane water electrolysis for hydrogen production.

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