A method for preparing an adaptive working condition electrolytic water catalyst based on dynamic reconfiguration programming
By applying a preset potential program to the water electrolysis catalyst for dynamic reconstruction, a thermodynamically stable heterogeneous interface is formed, which solves the problem of activity decay of statically designed catalysts in complex environments and achieves efficient and stable water electrolysis catalytic effect, making it suitable for industrial applications.
Patent Information
- Application Number
- CN202610298903.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-12
- Publication Date
- 2026-06-05
AI Technical Summary
Existing statically designed water electrolysis catalysts exhibit disordered and uncontrollable structural reconstruction under high overpotential and complex electrochemical environments, leading to rapid decay of catalytic activity and short service life, making it difficult to meet the requirements of long life, high stability, and high catalytic efficiency for industrial applications.
By applying a preset potential program in an electrochemical environment simulating actual working conditions, the pre-catalyst is driven to undergo directional and controllable electro-oxidative dynamic reconstruction, forming a thermodynamically stable heterogeneous interface. The phase transition sequence and kinetic rate of the multi-component catalyst are controlled by a step-potential sequence, thus constructing a highly active catalyst adapted to actual working conditions.
This method achieves long-term stable high activity and high stability of the catalyst under actual working conditions, significantly improves the catalytic effect, and has strong process compatibility, making it suitable for large-scale production and solving the bottleneck problem of traditional catalysts in industrial applications.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of catalytic material preparation technology, and in particular to a method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming. Background Technology
[0002] As the core pathway for green hydrogen production, water electrolysis technology can directly convert renewable energy sources such as solar and wind energy into hydrogen energy. It is a key technology for promoting the transformation of the energy structure towards cleaner and lower carbon emissions. Its commercialization and large-scale application have become an important breakthrough for the development of the hydrogen energy industry. Efficient and stable electrocatalysts are the core support for the application of water electrolysis technology.
[0003] For a long time, the development of electrocatalysts has followed a mainstream research paradigm centered on static material design. This paradigm focuses on the material preparation stage of catalysts, pre-constructing static material systems with optimized intrinsic activity through precise customization at the atomic and microstructure levels. Researchers have used various preparation methods, such as hydrothermal synthesis, high-temperature calcination, chemical vapor deposition, and electrodeposition, to selectively prepare multi-component materials such as metal oxides, phosphides, sulfides, and selenides, or nanomaterials with specific crystal configurations such as spinel and perovskite. By carefully designing and creating specific crystal faces, defect states, and heterojunctions, the number of catalytic active sites is increased, and the intrinsic activity of each active site is optimized through electronic structure regulation, theoretically improving catalytic performance. This static optimization design research approach has provided an effective technical path for the early exploration, development, performance iteration, and fundamental theoretical research of water electrolysis catalysts, and has also accumulated rich experience in material design and preparation for subsequent catalyst development.
[0004] However, as water electrolysis technology advances towards industrialization and large-scale application, existing statically designed catalyst systems are gradually revealing fundamental application defects. The pre-constructed fine microstructures struggle to maintain stability under the harsh conditions of real-world industrial electrochemical operation, becoming a core bottleneck restricting the industrial application of water electrolysis technology. Related research indicates that most statically designed water electrolysis catalysts undergo widespread and profound structural reconstruction on their surface and even in bulk under complex electrochemical environments with high overpotentials and strong oxidation / reduction. This reconstruction causes a significant deviation between the actual active sites on the catalyst surface and the initially designed active site state during actual operation, directly affecting catalytic performance. More critically, this structural reconstruction often exhibits spontaneous, disordered, and uncontrollable characteristics. Specific crystal faces, defect states, and heterogeneous interfaces constructed during the catalyst preparation stage are easily transformed into inactive phases during harsh operation, leading not only to rapid decay of catalytic activity but also a significant reduction in catalyst lifespan. This severe mismatch between the static design structure and the dynamic service structure makes it difficult for traditional catalysts to adapt to the continuous high current density operating conditions and complex and harsh service environments in industrial operation, and thus fails to meet the core requirements of industrial applications for long catalyst life, high stability, and high catalytic efficiency.
[0005] With the current industrialization of water electrolysis technology, there is an urgent need to overcome the limitations of traditional static material design and resolve the profound contradiction between static synthesis state design and dynamic service state evolution. Existing technologies lack design methods that can directly address, understand, and actively manage the structural reconstruction during catalyst service. Catalysts remain in an unpredictable, passive evolutionary state, making precise control over their structural evolution during service difficult. Against this backdrop, developing a novel catalyst design paradigm that transforms the catalyst's structural reconstruction process from passive and disordered to active and controllable, enabling the pre-design and precise control of the catalyst's service state and its formation process, is a necessary requirement for upgrading water electrolysis catalysts to industrial applications and a key to overcoming the industrialization bottleneck of water electrolysis technology. Summary of the Invention
[0006] The purpose of this invention is to provide an adaptive method for preparing water electrolysis catalysts based on dynamic reconfiguration programming, thereby addressing the problems existing in the prior art. This invention overcomes the limitations of traditional static material design by actively intervening in the service evolution process of the catalyst using electrochemical methods, thus constructing a thermodynamically stable heterogeneous interface with high intrinsic activity at the atomic scale in situ.
[0007] To achieve the above objectives, the present invention provides the following solution: This invention provides a method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming, comprising the following steps: The precatalyst is placed in an electrochemical environment simulating actual operating conditions, and a preset potential program is applied to drive the precatalyst to undergo directional and controllable electro-oxidative dynamic reconstruction to form a thermodynamically stable active layer; then the application of the potential program is stopped to obtain an electrocatalyst that adapts to operating conditions. The precatalyst is a single-component or multi-component heterostructure containing at least one electro-induced oxidation phase transition metal compound; The electrochemical environment includes at least an electrolyte system and an applied electric field consistent with actual operating conditions.
[0008] In this invention, the thermodynamically stable active layer is a metal hydroxide, a metal oxide, or a heterojunction thereof; preferably, it is a heterojunction formed from at least two of NiOOH, CoOOH, FeOOH, and MnOOH.
[0009] In this invention, the precatalyst is a precursor material that does not possess high catalytic activity (or only low activity) suitable for the target operating conditions, but can be transformed into a truly active catalytic species by controllable structural transformation (such as electro-induced oxidation dynamic reconstruction) under simulated / actual reaction / service conditions.
[0010] For metal compounds with multi-component heterostructures capable of electro-oxidative phase transitions, this invention induces spatiotemporally ordered relay reconstruction of different components by applying a step-like potential in the time dimension, thereby constructing a thermodynamically stable heterostructure with high intrinsic activity. The potential program used is a step-like potential sequence, which is used to regulate the phase transition sequence and kinetic rate of the pre-catalyst, so that the active layer forms an ordered heterostructure adapted to the actual working conditions.
[0011] To fundamentally resolve the deep-seated contradiction between static synthesis design and dynamic service evolution, this invention breaks through the limitations of traditional material design that focuses solely on structural optimization, proposing a novel dynamic reconfiguration programmed technology paradigm. The core design idea of this technology is to transform the passive structural evolution of catalysts during service into active interface construction. Through rationally designed electrochemical programmed methods, the structural reconfiguration process of the catalyst is actively guided, precisely controlled, and fully utilized, transforming this process into an effective way to construct highly active reaction interfaces.
[0012] Based on the fundamental principles of catalyst dynamic reconstruction, this invention matches precise electrochemical activation and operation programs to guide the catalytic material through a directional and controllable dynamic structural evolution along a pre-defined path during its service life. Ultimately, a highly active catalytic interface, highly adapted to actual operating conditions and dynamically stable during long-term operation, is spontaneously formed in situ. This invention comprehensively incorporates the service-state structure of the catalyst and its formation process into the scope of pre-design and precise control, achieving a technological paradigm leap from designing static catalytic materials to designing dynamic evolution processes and final service states.
[0013] For multi-component heterostructure precatalysts, the core of controlling the phase transition sequence and kinetic rate lies in relying on the differences in the inherent electro-oxidative phase transition characteristics of each component. Through precise design of a step-like potential sequence, the phase transition triggering timing and reaction rate of different components are differentiated and controlled, enabling each component to complete directional oxidation and reconstruction in a predetermined order, ultimately forming a thermodynamically stable, structurally ordered, and adaptable heterojunction active layer suitable for actual operating conditions. Before conducting potential control, in-situ Raman spectroscopy and in-situ XRD characterization techniques are used to determine the electro-oxidative phase transition initiation potential, peak potential, and complete phase transition potential of each metal compound component in the multi-component precatalyst, as well as the oxidation phase transition kinetic rate constant of each component at a specific potential. This clarifies the differences in phase transition potential and kinetic rate among the components. This fundamental characterization is a prerequisite for achieving precise phase transition control, ensuring that the subsequent potential program design matches the inherent characteristics of each component.
[0014] When using a stepped potential sequence modulation, fixed potential intervals are set in stages, and the potential holding time of each interval is precisely controlled to achieve sequential phase transition triggering of multiple components from low-potential to high-potential components, while simultaneously regulating the phase transition kinetic rate of each component. Specifically, the potential program is first divided into multiple potential stages matching the number of components. The first stage is set as the oxidation threshold potential interval of the low phase transition potential component, triggering only the electroinduced oxidation phase transition of this component, while the high phase transition potential component remains stable at this potential. After the low-potential component completes a preset degree of phase transition, the potential is stepped up to the oxidation threshold potential interval of the next component, triggering a relay-style phase transition of the next lowest potential component, and so on until all components have completed directional oxidation. At the same time, the holding time of the corresponding potential stage is designed according to the oxidation kinetic characteristics of each component. The holding time is shortened for components with fast oxidation phase transition rates to avoid over-oxidation and the formation of inactive phases; the holding time is extended for components with slow oxidation phase transition rates to ensure that they complete a sufficient and uniform phase transition to form the target active phase, thus achieving precise control of the phase transition kinetic rate of each component.
[0015] The regulation of the phase transition sequence and kinetic rate of the multi-component precatalyst ensures that the active phase generated by the oxidation of each component forms a layered and interlaced heterogeneous interface at the nanoscale, ensuring the synergistic effect of dual / multi-active sites. At the same time, the rate regulation ensures that the formed heterojunction is a thermodynamically stable structure that can exist stably for a long time in the harsh actual water electrolysis conditions without structural collapse or active phase peeling.
[0016] Furthermore, a three-electrode system is used to apply a preset potential program, with the pre-catalyst as the working electrode.
[0017] Furthermore, the potential program is a stepped potential program; the stepped potential program is divided into multiple potential stages that match the number of precatalyst components, each potential stage corresponds to the oxidation threshold potential range of a component, and is applied in a stepwise manner from low phase transition potential to high phase transition potential, thereby triggering the relay-type electro-induced oxidation phase transition of each component in sequence, and the holding time of each potential stage is designed according to the oxidation phase transition rate of the corresponding component.
[0018] Furthermore, the electrochemically oxidative phase-transformable metal compound is selected from at least one of metal phosphides, metal sulfides, metal nitrides, metal alloys, and metal oxides.
[0019] Furthermore, the metal in the electrochemically oxidative phase-transformable metal compound is at least one of Ni, Co, Fe, Mn, and Cu.
[0020] This invention utilizes programmed reconstruction to construct, in situ, a thermodynamically stable heterojunction (such as a NiOOH-CoOOH heterojunction) highly compatible with water electrolysis conditions in a simulated operating environment before the catalyst is put into actual service. This heterojunction is in its lowest energy state and loses the thermodynamic driving force for spontaneous transformation to the inactive phase under actual water electrolysis conditions, thereby fundamentally suppressing the destructive structural collapse of the catalyst. Simultaneously, the pre-catalyst undergoes structural reconstruction in an environment simulating the core characteristics of the operating conditions, forming a thermodynamically stable active structure adapted to actual conditions. This allows the resulting catalyst to directly match the core service conditions after being put into actual operation and to cope with minor fluctuations in operating conditions through microscopic dynamic equilibrium, achieving long-term stable and adaptable service.
[0021] Furthermore, the precatalyst is a NiO-CoP composite catalyst.
[0022] Furthermore, in a 1M KOH alkaline electrolyte, the NiO-CoP composite catalyst was subjected to the following step-potential program: S1. Induction period: Maintain at 1.20~1.30 V (vs. RHE) for 5~60 min to drive the preferential oxidation of CoP to generate the CoOOH active layer; S2. Nucleation period: Step to 1.35~1.40 V (vs. RHE) and hold for 5~60 min to trigger NiO relay oxidation to generate NiOOH phase; S3. Steady-state period: Step to 1.70~1.75V (vs. RHE) and hold for 5~60min to promote the atomic-level fusion of CoOOH and NiOOH to form a thermodynamically steady-state active layer of NiOOH-CoOOH ordered heterojunction.
[0023] Furthermore, the NiO-CoP composite catalyst is preferably prepared via the following steps: (1) Conductive substrate pretreatment: The nickel mesh was ultrasonically treated with dilute hydrochloric acid, acetone and ethanol in sequence, then cleaned with deionized water and vacuum dried. (2) CoP nanostructure electrodeposition: Using a pretreated nickel mesh as the working electrode, in a precursor solution containing CoCl2•6H2O, NaH2PO2•H2O, and NH4Cl, at 50 mA cm⁻¹ -2 Electrodeposition was performed at a constant current density for 1–10 min, followed by cleaning and drying to obtain a CoP electrode; (3) NiO-CoP composite construction: Using the CoP electrode prepared in step (2) as the working electrode, in Ni(NO3)2•6H2O aqueous solution, -10 mA cm -2 Electrodeposition was performed at the current density for 10 s, followed by cleaning and drying, and then heat treatment at 300 °C for 1 h in an Ar atmosphere to obtain the NiO-CoP composite catalyst.
[0024] In step (2), the precursor solution contains 0.1 M CoCl2•6H2O, 0.25 M NaH2PO2•H2O, and 0.3 M NH4Cl, and the pH of the precursor solution is adjusted to 3.0 with 37 wt.% HCl.
[0025] In step (3), the concentration of the Ni(NO3)2•6H2O aqueous solution is 5 mM.
[0026] The present invention also provides an adaptive water electrolysis catalyst prepared by the above preparation method.
[0027] The present invention further provides the application of the above-mentioned adaptive operating condition water electrolysis catalyst in the field of water electrolysis.
[0028] The present invention discloses the following technical effects: The water electrolysis catalyst prepared by this invention possesses both excellent catalytic performance and ultra-high industrial-grade stability, while also exhibiting strong process compatibility and industrialization potential. Relying on the optimized electronic structure and abundant active sites constructed through programmed reconstruction, the catalyst displays rapid reaction kinetics in the oxygen evolution reaction, resulting in significant catalytic effects. The thermodynamically stable heterojunction formed through programmed induction is in the lowest energy state, fundamentally eliminating the driving force for spontaneous transformation to the inactive phase, thus solving the industry bottleneck of poor service performance of traditional catalysts.
[0029] The catalyst of this invention undergoes directional reconstruction under simulated operating conditions. After being put into actual operating conditions, it can be directly adapted to the core service conditions. Through microscopic dynamic equilibrium and the synergistic response of active sites at heterogeneous interfaces, it can cope with small fluctuations in operating conditions and achieve long-term stable and efficient service.
[0030] The electrodeposition and in-situ electrochemical processing technology used in this invention is highly compatible with existing industrial electrode preparation processes. It can be connected to existing production lines by simply adding a programmed electrochemical reconstruction module. Moreover, the precursor is inexpensive, the operation is simple and easy to control, there are no harsh reaction conditions, and it can achieve large-scale production. It has extremely high industrial application value and broad prospects for promotion. Attached Figure Description
[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments 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.
[0032] Figure 1 The images show the morphology and structure of the NiO-CoP composite catalyst in Example 1, where a is a SEM image, b is an XRD image, and c is an EDS image.
[0033] Figure 2 This is an in-situ Raman spectral monitoring image of the NiO-CoP composite catalyst and CoP material dynamically reconstructed during the oxygen evolution reaction in Example 1.
[0034] Figure 3 The image shows the active heterostructure interface of the NiOOH-CoOOH ordered heterojunction water electrolysis catalyst in Example 1, as represented by a TEM image.
[0035] Figure 4 The polarization curve (a) and Tafel slope curve (b) of the oxygen evolution reaction of the NiOOH-CoOOH ordered heterojunction water electrolysis catalyst in Example 1 are shown.
[0036] Figure 5 The image shows the long-term stability curves of the NiOOH-CoOOH ordered heterojunction water electrolysis catalyst (anode) and the commercial Raney nickel (cathode) system in Example 1 under industrial-grade high current density water electrolysis.
[0037] Figure 6 The image shows the X-ray diffraction pattern of the carbon cloth-based NiO-CoP nanowire catalytic material in Example 2.
[0038] Figure 7 The image shows the elemental distribution of the carbon cloth-based NiO-CoP nanowire catalytic material in Example 2 using EDS energy dispersive spectroscopy.
[0039] Figure 8 The image shows the active heterojunction interface characterization of the carbon cloth-based NiOOH-CoOOH heterojunction water electrolysis catalyst in Example 2. Detailed Implementation
[0040] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0041] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0042] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0043] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.
[0044] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.
[0045] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.
[0046] Example 1 In this embodiment, a NiO-CoP composite catalyst is used as a precatalyst. Through dynamic reconstruction programmed design, a highly active and stable nano-heterojunction water electrolysis catalyst is constructed in situ. The steps are as follows: (1) Pretreatment of conductive substrate Commercial nickel mesh (1×2cm) was selected. 2 Using this as the electrode substrate, it was ultrasonically treated with dilute HCl solution, acetone, and ethanol for 10 minutes each in sequence to thoroughly remove surface oxides and organic contaminants. Finally, it was washed with deionized water and vacuum dried for later use.
[0047] (2) Electrodeposition synthesis of CoP nanostructures Electrodeposition was carried out using a three-electrode electrochemical system, wherein the working electrode was the nickel mesh pretreated in step (1), and another identical nickel mesh was used as the counter electrode, and the reference electrode was an Ag / AgCl electrode.
[0048] Preparation of precursor solution: Weigh appropriate amounts of CoCl2•6H2O, NaH2PO2•H2O, and NH4Cl, dissolve them in deionized water, and prepare a mixed solution containing 0.1M CoCl2•6H2O, 0.25M NaH2PO2•H2O, and 0.3M NH4Cl. Adjust the pH of the solution to 3.0 with 37wt.% HCl to obtain the precursor solution. The three electrodes were completely immersed in the precursor solution, and a constant current density of 50 mA cm⁻¹ was set. -2 Electrodeposition was performed for 5 minutes. After electrodeposition, the working electrode was removed, cleaned with deionized water, and dried to obtain a CoP electrode with a uniform CoP nanostructure layer grown on its surface.
[0049] (3) Construction of NiO-CoP composite catalyst Using the CoP electrode prepared in step (2) as the working electrode, the nickel mesh as the counter electrode, and Ag / AgCl as the reference electrode, a three-electrode system was built again. The three electrodes were placed in 150 mL of a 5 mM Ni(NO3)2•6H2O aqueous solution, and the current density was set to -10 mA cm⁻¹. -2 Electrodeposition for 10 seconds; After electrodeposition, the electrode was removed and washed with deionized water and ethanol in sequence, and then dried in a vacuum drying oven at 60°C for 10 hours. Subsequently, the dried electrode was placed in a tube furnace and heat-treated at 300°C for 1 hour under Ar atmosphere protection. After natural cooling, the NiO-CoP composite electrode (NiO-CoP composite catalyst) was obtained.
[0050] Figure 1 The images show the morphology and structure of the NiO-CoP composite catalyst in Example 1, confirming that NiO and CoP are uniformly composited on a nickel mesh substrate; where a is a SEM image, b is an XRD image, and c is an EDS image.
[0051] (4) Programmatic dynamic reconstruction preparation of NiOOH-CoOOH ordered heterojunction water electrolysis catalyst The NiO-CoP composite electrode was placed in a 1M KOH electrolyte and subjected to in-situ Raman spectroscopy. Figure 2 Monitor the entire reconstruction process and, based on Figure 2The phase transition potential law of NiO-CoP electro-oxidation was characterized, and a segmented constant potential program was executed: Figure 2 The in-situ Raman spectra of the dynamic reconstruction of the oxygen evolution reaction between the NiO-CoP composite catalyst and CoP material are presented. In a 1M KOH electrolyte, a series of constant potentials of 1.0 V, 1.1 V, 1.2 V, 1.25 V, 1.3 V, 1.35 V, 1.4 V, 1.5 V, 1.6 V, and 1.7 V (vs. RHE) were applied to CoP and NiO-CoP, and the in-situ Raman spectra at different potentials were measured to study the sensitive potential range of the material's reconstruction evolution. The results show that neither CoP nor NiO-CoP exhibits a reconstruction response at 1.0 V and 1.1 V. CoP begins to reconstruct and generate CoOOH at potentials of 1.3 V and above, while NiO-CoP begins to reconstruct and generate CoOOH at 1.2 V. Furthermore, NiO initiates a relay-style reconstruction to generate NiOOH at potentials of 1.35 V and above. This clarifies the potential difference in the electroinduced oxidation phase transition between the two, providing a basis for the design of potential ranges in segmented constant potential programs.
[0052] The following segmented potential-stable procedure was performed on the NiO-CoP composite electrode: Phase I (Induction Period - Preferential Surface Oxidation): A potential of 1.20V (vs. RHE) was applied and held for 5 min, and a value of 495 cm⁻¹ was observed. -1 590cm -1 Characteristic peaks indicate the formation of a CoOOH active layer; in this stage, the lower oxidation barrier of CoP drives the CoP component to preferentially undergo surface oxidation, generating a defect-rich CoOOH active layer. Stage II (Nucleation Phase - Relay Reconfiguration): The potential was stepped to 1.35V (vs. RHE) and held for 10 min. A value of 475 cm⁻¹ was detected. -1 555cm -1 Characteristic peaks indicate that NiO undergoes a phase transformation to form the NiOOH phase. The local high-valence chemical microenvironment created by the CoOOH layer formed in stage I lowers the oxidation energy barrier of adjacent NiO components, triggering a relay phase transformation, which gradually transforms into the NiOOH phase. Phase III (Steady-state period - interface construction and fusion): The potential was increased to 1.70V (vs. RHE) and held for 5 min. The peak shapes of each characteristic peak were monitored to be stable, indicating that the NiOOH and CoOOH interface achieved atomic-level fusion and lattice matching. After the program was completed, an in-situ NiOOH-CoOOH ordered heterojunction water electrolysis catalyst was obtained.
[0053] The NiOOH-CoOOH ordered heterojunction water electrolysis catalyst prepared in this embodiment was subjected to electrochemical performance testing of oxygen evolution reaction (OER) in water electrolysis. The test environment was a 1 M KOH alkaline electrolyte. The specific test results are as follows: at 10 mA cm⁻¹ -2 At the given current density, the oxygen evolution reaction overpotential of this catalyst is as low as 208 mV, and the Tafel slope is 43 mV dec. -1 It exhibits excellent electrocatalytic reaction kinetics.
[0054] Under industrial-grade conditions of 30% KOH electrolyte and 80°C, an application of 500 mA cm⁻¹ was applied. -2 The catalyst was subjected to continuous service stability tests at high current density. During the test, the catalyst cell voltage remained stable at 1.761 V. After 500 hours of continuous stable operation, there was no significant decay in catalytic activity and no significant drift in potential, demonstrating industrial-grade long-term service stability far exceeding that of traditional water electrolysis catalysts.
[0055] This embodiment utilizes the difference in oxidation potential between NiO and CoP, and drives their evolution along a preset kinetic path by hierarchically controlling the external electric field: preferentially inducing oxidation of the CoP surface in the low overpotential range to construct a local chemical microenvironment; then triggering the relay reconstruction of NiO in the high overpotential range, and finally achieving atomic-level fusion of the two phases in the high potential range, successfully constructing a thermodynamically stable NiOOH-CoOOH ordered heterojunction within the confined space of the nickel mesh substrate. The resulting catalyst can be directly adapted to the industrial-grade service conditions of water electrolysis.
[0056] Figure 3 The image shows the TEM characterization of the active heterostructure interface of the NiOOH-CoOOH ordered heterojunction water electrolysis catalyst in Example 1. The crystal plane structure and interface fusion state of NiOOH and CoOOH were observed, confirming the successful construction of the atomic-level heterostructure interface.
[0057] Figure 4 The images show the oxygen evolution reaction polarization curve (a) and Tafel slope curve (b) of the NiOOH-CoOOH ordered heterojunction water electrolysis catalyst in Example 1. It can be seen that the NiOOH-CoOOH catalyst prepared in this invention has a lower overpotential and Tafel slope compared with single CoOOH, and its catalytic activity is significantly improved.
[0058] Figure 5 The image shows the long-term stability curves of the NiOOH-CoOOH ordered heterojunction water electrolysis catalyst (anode) and the commercial Raney nickel (cathode) system in Example 1 under industrial-grade high current density. The catalyst exhibits excellent industrial-grade stability with no significant potential drift during 500 hours of continuous operation.
[0059] Example 2 In this embodiment, a NiO-CoP composite catalyst obtained through hydrothermal and high-temperature heat treatment is used as a precatalyst. Through dynamic reconstruction programmed design, a highly active and stable nano-heterojunction water electrolysis catalyst is constructed in situ. The steps are as follows: (1) Pretreatment of conductive substrate Commercial carbon cloth (2×3 cm) was selected. 2 Using concentrated sulfuric acid solution, deionized water and ethanol as electrode substrates, the carbon cloth was ultrasonically treated for 10 minutes each in sequence to make the surface of the carbon cloth more hydrophilic and remove organic pollutants. Finally, it was vacuum dried for later use.
[0060] (2) Synthesis of CoP nanostructures Weigh 0.2500 g of cobalt nitrate hexahydrate, 0.1200 g of ammonium fluoride, and 0.5000 g of urea, and add them to 35 mL of deionized water and stir until homogeneous. Place the treated carbon cloth into the prepared solution, then react it in a 50 mL hydrothermal reactor at 120 °C for 8 h. After cooling to room temperature, wash with deionized water and ethanol sequentially for 10 min each, and then place it in a forced-air drying oven at 60 °C for 4 h to generate Co(OH)₂ nanowires. Further phosphating treatment is performed in a tube furnace. Place the sample in the center of the tube furnace, weigh 1.0000 g of sodium hypophosphite monohydrate and place it upstream of the furnace. Under a mixed atmosphere of 280 sccm argon and 20 sccm hydrogen, the heating rate is 3 °C / min. -1 CoP nanowires were obtained by heating at 300℃ for 1 h and then cooling to room temperature. (3) Construction of NiO-CoP composite catalyst: Nickel oxide nanoparticles were deposited on the CoP surface using a thermal decomposition method. Ni(NO3)2·6H2O (29.0 mg) was dissolved in 10.0 mL of ethanol by magnetic stirring and ultrasonic treatment to obtain a light green solution with a concentration of 0.01 M. Then, 200 µL of the precursor solution was coated onto the surface of a CoP sample (2 cm × 3 cm) grown on a carbon cloth substrate and dried at room temperature. The resulting CoP substrate containing the nickel precursor was then dried at 400 °C under an argon atmosphere. o Heating at C for 2 hours formed a NiO-CoP sample, exhibiting a nanowire morphology. See [link to XRD pattern and EDS diagram of the specific phase structure]. Figure 6 and Figure 7 .
[0061] (4) Programmatic Dynamic Reconstruction of Customized NiOOH-CoOOH Active Heterojunction: The NiO-CoP composite electrode was placed in 1 MKOH electrolyte. Stage I (Induction Period - Preferential Surface Oxidation): The surface oxidation of the CoP component was preferentially driven at 1.25 V (vs. RHE) for 5 min. Stage II (Nucleation Period - Relay Reconstruction): The voltage was increased to 1.40 V (vs. RHE) and held for 10 min. This stage triggered a relay phase transition of NiO, which gradually transformed into the NiOOH phase. Stage III (Steady-State Period - Interface Construction and Fusion): The interface was held at a high potential of 1.75 V (vs. RHE) for 5 min. This promoted deep atomic-level fusion and lattice matching between the NiOOH and CoOOH phases, ultimately constructing a highly active NiOOH-CoOOH heterojunction structure in situ. The active heterojunction is shown in [reference needed]. Figure 8 .
[0062] The catalyst prepared by this invention possesses both excellent catalytic performance and ultra-high industrial-grade stability, while also exhibiting strong process compatibility and industrialization potential. Based on the optimized electronic structure and abundant active sites constructed through programmed reconstruction, this catalyst displays rapid reaction kinetics in the oxygen evolution reaction, significantly improving catalytic efficiency. The heterogeneous interface formed through programmed induction is a thermodynamically stable structure. Through microscopic dynamic equilibrium and the synergistic optimization of the catalytic pathway by multiple metal active sites at the heterogeneous interface, it addresses minor fluctuations in operating conditions, fundamentally solving the industry bottleneck problem of short service life of traditional catalysts.
[0063] The electrodeposition and in-situ electrochemical treatment process employed in this invention is highly compatible with existing industrial electrode preparation processes. The preparation process can be directly integrated into existing industrial production lines for water electrolysis electrodes. Only a programmed electrochemical reconstruction module needs to be added to the production line, setting a potential-time program matched to the material, to achieve large-scale catalyst preparation. Furthermore, the precursor materials are inexpensive to procure, the process is simple and easy to control, requiring no expensive and complex equipment, and avoiding harsh reaction conditions such as high temperature and high pressure. It is perfectly suited to the needs of large-scale industrial production, possessing extremely high industrial application value and broad prospects for promotion.
[0064] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims
1. A method for preparing an adaptive water electrolysis catalyst based on dynamically reconfigurable programmed operation, characterized in that, Includes the following steps: The precatalyst is placed in an electrochemical environment that simulates the characteristics of actual working conditions. A preset potential program is applied to drive the precatalyst to undergo electro-oxidative dynamic reconstruction, forming a thermodynamically stable active layer. After that, the application of the potential program is stopped, and an adaptive working condition water electrolysis catalyst is obtained. The precatalyst is a single-component or multi-component heterostructure containing at least one electro-induced oxidation phase transition metal compound; The electrochemical environment includes at least an electrolyte system and an applied electric field consistent with actual operating conditions.
2. The method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming according to claim 1, characterized in that, A preset potential program is applied using a three-electrode system, with the pre-catalyst as the working electrode.
3. The method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming according to claim 1, characterized in that, The potential program is a stepped potential program; the stepped potential program is divided into multiple potential stages that match the number of precatalyst components. Each potential stage corresponds to the oxidation threshold potential range of a component. The potentials are applied in a stepwise manner from low phase transition potential to high phase transition potential, thereby triggering the relay-type electro-induced oxidation phase transition of each component in sequence. The holding time of each potential stage is designed according to the oxidation phase transition rate of the corresponding component.
4. The method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming according to claim 1, characterized in that, The electro-oxidative phase-transformable metal compound is selected from at least one of metal phosphides, metal sulfides, metal nitrides, metal alloys, and metal oxides.
5. The method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming according to claim 4, characterized in that, The metal in the electro-oxidative phase transition metal compound is at least one of Ni, Co, Fe, Mn, and Cu.
6. The method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming according to claim 1, characterized in that, The precatalyst is a NiO-CoP composite catalyst.
7. The method for preparing an adaptive water electrolysis catalyst based on dynamic reconfiguration programming according to claim 6, characterized in that, The NiO-CoP composite catalyst was subjected to the following step-potential program in a 1M KOH alkaline electrolyte: S1. Induction period: Maintain at 1.20~1.30 V (vs. RHE) for 5~60 min to drive the preferential oxidation of CoP to generate the CoOOH active layer; S2. Nucleation period: Step to 1.35~1.40 V (vs. RHE) and hold for 5~60 min to trigger NiO relay oxidation to generate NiOOH phase; S3. Steady-state period: Step to 1.70~1.75V (vs. RHE) and hold for 5~60min to promote the atomic-level fusion of CoOOH and NiOOH to form a thermodynamically steady-state active layer of NiOOH-CoOOH ordered heterojunction.
8. The adaptive water electrolysis catalyst prepared by the preparation method according to any one of claims 1-7.
9. The application of the adaptive operating condition water electrolysis catalyst as described in claim 8 in the field of water electrolysis.