High Oxygen Evolution Reaction Research Articles

Computational screening of Group VⅢ@C5N4 single-atom electrocatalysts for overall water splitting

Single-atom catalysts (SACs) have great potential for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) since their high atomic utilization and strong metal–support interactions. Herein, we develop TM@C5N4 (TM = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt) catalysts via embedding Group VⅢ TM in holey C5N4 substrate and further evaluate their electrocatalytic activity using density functional theory (DFT) calculations. Systematical studies indicate that Fe@C5N4, Pd@C5N4 and Ir@C5N4 catalysts all exhibit excellent HER performance, which mainly because of their small ΔGH* values of 0.101 eV, -0.114 eV and 0.070 eV, respectively. In parallel, Rh@C5N4 and Ir@C5N4 possess high OER activity along with low overpotential of 0.50 V, which is superior to the commercial IrO2 catalyst (0.56 V). Obviously, Ir@C5N4 could be utilized as bifunctional electrocatalysts both HER and OER in water splitting. Furthermore, we analyze their correlative catalytic mechanisms using the molecular orbitals. Besides, biaxial strain modulation could effectively regulate the catalytic activity of HER and OER. Particularly, 2 % biaxial tensile strain could bring Ir@C5N4 superb HER/OER catalytic performance. Finally, we anticipate that this strain engineering would provide a new perspective for developing high-performance SACs for water splitting.

Achieving High OER Performance by Tuning the Co/Mn Content in Prussian Blue Analogues.

The need for efficient, economical, and clean energy systems is increasing, and as a result, interest in water-splitting techniques to produce green hydrogen is also increasing. However, the sluggish kinetics of the oxygen evolution reaction (OER) hinders the practical application and widespread use of water-splitting technologies; therefore, to address this challenge, it is essential to develop cost-effective and efficient OER catalysts. In this work, we have synthesized an inexpensive and tunable FeCoMn Prussian blue analogue (PBAs) as an efficient OER catalyst via a straightforward process. The ratio of the Co and Mn to optimize the electrochemical performance, and as a result, the FeCo0.41Mn0.42 PBA catalyst demonstrated the best electrochemical performance (260/304 mV overpotential at 10/50 mA cm-2, a low Tafel slope of 48 mV dec-1 and a good stability of 72 h at 10 mA cm-2). Additionally, X-ray absorption spectroscopy (XAS) measurements and density functional theory (DFT) calculations suggest that the FeCo0.41Mn0.42 PBA possesses the optimized electronic density distribution at the active site (Co), and the doping of Mn and Fe can not only increase the electricity conductivity but also activate the critical H2O deprotonation step.

Valence Band-Tunable NiFe Electrocatalyst Triggered by the Dynamic Mo Exudation and Re-Deposition for Superior High Current Density Oxygen Evolution Reaction.

Developing energy- and time-efficient strategies to derive high-performance non-precious electrocatalysts for anodic oxygen evolution reaction (OER), especially stably working at industrial-demanding current density, is still a big challenge. In this work, a concise molten salt erosion scenario was devised to rapidly modulate the smooth surface of the commercial NiMo foam substrate into the rough, electronically coupled, and hierarchically porous Ni/Fe/Mo(oxy)hydroxide catalyst layer assembled by the nanosphere array. This self-supported catalyst is super-hydrophilic for the alkaline electrolyte and distinguished by a balanced Mo leaching/surface-readsorption process to tune the metal d band center and electronic perturbation. The altered electronic environment with the favored OER intermediate adsorption behavior attains the outstanding OER activity in terms of a very small overpotential of 230.21 mV at 10 mA cm-2 and an ultra-long stability for 1179.45 h to sustain the initial commercial-level current density of ca. 1000 mA cm-2. This superb performance transcends most of the edge-cutting transition metal peers reported recently and can satisfy the standards of industrial applications. This industrial-compatible synthesis technology holds profound implications for hydrogen production via water splitting and other electrochemical applications.

Fluorine‐Lodged High‐Valent High‐Entropy Layered Double Hydroxide for Efficient, Long‐Lasting Zinc‐Air Batteries

AbstractEfficient and stable bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts are urgently needed to unlock the full potential of zinc‐air batteries (ZABs). High‐valence oxides (HVOs) and high entropy oxides (HEOs) are suitable candidates for their optimal electronic structures and stability but suffer from demanding synthesis. Here, a low‐cost fluorine‐lodged high‐valent high‐entropy layered double hydroxide (HV‐HE‐LDH) (FeCoNi2F4(OH)4) is conveniently prepared through multi‐ions co‐precipitation, where F− are firmly embedded into the individual hydroxide layers. Spectroscopic detections and theoretical simulations reveal high valent metal cations are obtained in FeCoNi2F4(OH)4, which enlarge the energy band overlap between metal 3d and O 2p, enhancing the electronic conductivity and charge transfer, thus affording high intrinsic OER catalytic activity. More importantly, the strengthened metal‐oxygen (M−O) bonds and stable octahedral geometry (M−O(F)6) in FeCoNi2F4(OH)4 prevent structural reorganization, rendering long‐term catalytic stability. Furthermore, an efficient three‐phase reaction interface with fast oxygen transportation was constructed, significantly improving the ORR activity. ZABs assembled with FeCoNi2F4(OH)4@HCC (hydrophobic carbon cloth) cathodes deliver a top performance with high round‐trip energy efficiency (61.3 % at 10 mA cm−2) and long‐term stability (efficiency remains at 58.8 % after 1050 charge–discharge cycles).

Fluorine-lodged high-valent high-entropy layered double hydroxide for efficient, long-lasting zinc-air batteries.

Efficient and stable bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts are urgently needed to unlock the full potential of zinc-air batteries (ZABs). High-valence oxides (HVOs) and high entropy oxides (HEOs) are suitable candidates for their optimal electronic structures and stability but suffer from demanding synthesis. Here, a low-cost fluorine-lodged high-valent high-entropy layered double hydroxide (HV-HE-LDH) (FeCoNi2F4(OH)4) is conveniently prepared through multi-ions co-precipitation, where F- are firmly embedded into the individual hydroxide layers. Spectroscopic detections and theoretical simulations reveal high valent metal cations are obtained in FeCoNi2F4(OH)4, which enlarge the energy band overlap between metal 3d and O 2p, enhancing the electronic conductivity and charge transfer, thus affording high intrinsic OER catalytic activity. More importantly, the strengthened metal-oxygen (M-O) bonds and stable octahedral geometry (M-O(F)6) in FeCoNi2F4(OH)4 prevent structural reorganization, rendering long-term catalytic stability. Furthermore, an efficient three-phase reaction interface with fast oxygen transportation was constructed, significantly improving the ORR activity. ZABs assembled with FeCoNi2F4(OH)4@HCC (hydrophobic carbon cloth) cathodes deliver a top performance with high round-trip energy efficiency (60.6% at 10 mA cm-2) and long-term stability (efficiency remains at 58.8% after 1050 charge-discharge cycles).

Oxyanion Engineering on RuO2 for Efficient Proton Exchange Membrane Water Electrolysis.

In acidic proton exchange membrane water electrolysis (PEMWE), the anode oxygen evolution reaction (OER) catalysts rely heavily on the expensive and scarce iridium-based materials. Ruthenium dioxide (RuO2) with lower price and higher OER activity, has been explored for the similar task, but has been restricted by the poor stability. Herein, we developed an anion modification strategy to improve the OER performance of RuO2 in acidic media. The designed multicomponent catalyst based on sulfate anchored on RuO2/MoO3 displays a low overpotential of 190 mV at 10 mA cm-2 and stably operates for 500 hours with a very low degradation rate of 20 μV h-1 in acidic electrolyte. When assembled in a PEMWE cell, this catalyst as an anode shows an excellent stability at 500 mA cm-2 for 150 h. Experimental and theoretical results revealed that MoO3 could stabilize sulfate anion on RuO2 surface to suppress its leaching during OER. Such MoO3-anchored sulfate not only reduces the formation energy of *OOH intermediate on RuO2, but also impedes both the surface Ru and lattice oxygen loss, thereby achieving the high OER activity and exceptional durability.

Nanostructured Fe-Doped Ni3S2 Electrocatalyst for the Oxygen Evolution Reaction with High Stability at an Industrially-Relevant Current Density.

A novel oxygen evolution reaction (OER) electrocatalyst was prepared by a synthesis strategy consisting of the solvothermal growth of Ni3S2 nanostructures on Ni foam, followed by hydrothermal incorporation of Fe species (Fe-Ni3S2/Ni foam). This electrocatalyst displayed a low OER overpotential of 230 mV at 100 mA·cm-2, a low Tafel slope of 43 mV·dec-1, and constant performance at an industrially relevant current density (500 mA·cm-2) over 100 h in a 1.0 M KOH electrolyte, despite a minor loss of Fe in the process. Based on a detailed characterization by (in situ) Raman spectroscopy, (quasi-in situ) XPS, SEM, TEM, XRD, ICP-AES, EIS, and Cdl analysis, the high OER activity and stability of Fe-Ni3S2/Ni foam were attributed to the nanostructuring of the surface in the form of stable nanosheets and to the combination of Ni3S2 granting suitable electrical conductivity with newly formed NiFe-based (oxy)hydroxides at the surface of the material providing the active sites for OER.

High-Entropy Selenides with Tunable Lattice Distortion as Efficient Electrocatalysts for Oxygen Evolution Reaction.

Developing stable and active electrocatalysts is crucial for enhancing the oxygen evolution reaction (OER) efficiency, which sluggish kinetics hinders sustainable hydrogen production. High entropy selenides (HESes) features with random distribution of multiple metals cations and unique electronic and size effect of Se anion, allowing for precious regulation of their catalytic properties towards high OER activity. In this work, we report a series of high-entropy selenides catalysts with tunable lattice strain for electrocatalytic oxygen evolution. Electrochemical measurements show that the quinary (NiCoMnMoFe)Sex requires only 291 mV to reach 10 mA cm-2 and exhibits a superior stability with negligible current decay during 100 h's continuous operation. By combining experimental measurements and theoretical calculation, the study reveals that the lattice distortion, reflected by the local microstrain near the active site, plays a vital role in boosting the OER activity of HESes.

Stabilization of High-Valent Molecular Cobalt Sites through Oxidized Phosphorus in Reduced Graphene Oxide for Enhanced Oxygen Evolution Catalysis.

Heterogeneous molecular cobalt (Co) sites represent one type of classical catalytic sites for electrochemical oxygen evolution reaction (OER) in alkaline solutions. There are dynamic equilibriums between Co2+, Co3+ and Co4+ states coupling with OH-/H+ interaction before and during the OER event. Since the emergence of Co2+ sites is detrimental to the OER cycle, the stabilization of high-valent Co sites to shift away from the equilibrium becomes critical and is proposed as a new strategy to enhance OER. Herein, phosphorus (P) atoms were doped into reduced graphene oxide to link molecular Co2+ acetylacetonate toward synthesizing a novel heterogeneous molecular catalyst. By increasing the oxidation states of P heteroatoms, the linked Co sites were spontaneously oxidized from 2+ to 3+ states in a KOH solution through OH- ions coupling at an open circuit condition. With excluding the Co2+ sites, the as-derived Co sites with 3+ initial states exhibited intrinsically high OER activity, validating the effectiveness of the strategy of stabilizing high valence Co sites.

Integration of Multifunctionality in a Colloidal Self‐Repairing Catalyst for Alkaline Water Electrolysis to Achieve High Activity and Durability

Self‐repairing catalysts are useful for achieving alkaline water electrolyzers with long lifetimes under intermittent operation. However, rational methodologies for designing self‐repairing catalysts have not yet been established. Herein, hybrid cobalt hydroxide nanosheets (Co‐ns), with a high deposition (repairing) rate, and β‐FeOOH nanorods (Fe‐nr), with high oxygen evolution reaction (OER) ability, are electrostatically self‐assembled into composite catalysts. This strategy is developed to integrate multifunctionality in self‐repairing catalysts. Positively charged Co‐ns and negatively charged Fe‐nr form uniform composites when dispersed in an electrolyte. These composites are electrochemically deposited on a nickel electrode by electrolysis at 800 mA cm−2. Co‐ns form a conductive mesoporous assembly of CoOOH nanosheets as a support. Fe‐nr are then distributed on the CoOOH nanosheets as active sites for the OER. Because of the high deposition rate of Co‐ns, the amount of Fe‐nr deposited increases 22 times compared to when Fe‐nr is deposited alone, and the OER current density increases 14 times compared to that of Co‐ns alone. The composite self‐repair catalyst shows the highest activity and durability under an accelerated durability test (ADT), and its degradation rate decreases from 84 μV cycle−1 (Fe‐nr only) to 60 μV cycle−1 (composite catalyst) under ADT conditions without repair.

A facile synthesis of N-doped carbon encapsulated multimetallic carbonitride as a robust electrocatalyst for oxygen evolution reaction

Electrocatalytic water splitting is a promising solution for generating clean hydrogen. Transition metal compounds are among the most extensively investigated catalysts developed to date for water oxidation in alkaline media, a process also known as the oxygen evolution reaction (OER). However, the application of these catalysts was constrained by insufficient stability arising from surface oxidation and metal dissolution under high OER potential. In this work, we developed a facile approach using urea-based gel as the precursor of preparing a series of multimetallic carbonitride particles which were encapsulated by N-doped carbon (NC). In particular, (MoCoFeNiZr)CN@NC core–shell structure delivered a low overpotential of 246 mV at a current density of 10 mA cm−2 in 1 M KOH during OER. Importantly, operando differential electrochemical mass spectrometry (DEMS), together with multiple microscopic and spectroscopic analyses, indicated that the NC shells effectively maintained the crystalline stability of carbonitride via suppressing the surface reconstruction during catalysis. The highly graphitic NC also demonstrates excellent stability against oxidation. This work shows a promising strategy of stabilizing electrocatalyst at high anodic potential, paving the way for the development of robust electrode materials for energy conversion.

Enriched Oxygen Coverage Localized within Ir Atomic Grids for Enhanced Oxygen Evolution Electrocatalysis.

Inefficient active site utilization of oxygen evolution reaction (OER) catalysts have limited the energy efficiency of proton exchange membrane (PEM) water electrolysis. Here, an atomic grid structure is demonstrated composed of high-density Ir sites (≈10atoms per nm2) on reactive MnO2-x support which mediates oxygen coverage-enhanced OER process. Experimental characterizations verify the low-valent Mn species with decreased oxygen coordination in MnO2-x exert a pivotal impact in the enriched oxygen coverage on the surface during OER process, and the distributed Ir atomic grids, where highly electrophilic Ir─O(II-δ)- bonds proceed rapidly, render intense nucleophilic attack of oxygen radicals. Thereby, this metal-support cooperation achieves ultra-low overpotentials of 166mV at 10mA cm-2 and 283mV at 500mA cm-2, together with a striking mass activity which is 380 times higher than commercial IrO2 at 1.53V. Moreover, its high OER performance also markedly surpasses the commercial Ir black catalyst in PEM electrolyzers with long-term stability.

Boosting OER activity of Fe-N Moieties via Ni induced d-Orbital Tailoring for durable rechargeable Zn-Air batteries

Fe-N-C-based catalysts are considered the most promising Pt candidates due to their high oxygen reduction reaction (ORR) activity and low cost, whereas their oxygen evolution reaction (OER) performance is extremely poor due to the sluggish O-O coupling process, which hampers the practical application of rechargeable zinc-air batteries. Here, we in situ infiltrate Ni and Fe ions into metal triazolidine (MET)-derived N-doped porous carbon via a microporous confinement-pyrolysis strategy to enhance the OER activity of the Fe-N sites. The introduction of Ni induced the electronic delocalization of Fe atoms at the Fe-N center, which lowered the adsorption energy barriers for the decisive velocity step (O*→OOH*), thus accelerating the O-O bond coupling and OER kinetics. In addition, the preferential formation of NiOOH at high OER potentials ensures the catalytic stability of zinc-air batteries by trapping Fe ions escaping from carbon corrosion to form FeOOH. The optimized catalyst (FeNi-NC) has an overpotential of only 351 mV at a current density of 50 mA cm−2 under alkaline conditions. More importantly, the assembled ZABs can be stably charged and discharged for more than 500 h at 10 mA cm−2, demonstrating excellent battery charging and discharging stability. This work shows the great potential of strong electronic interactions between polymetals to improve Fe-N-C catalysts.

Defects trigger redox reactivities between metal and lattice oxygen in high-entropy layered double hydroxide for boosting oxygen evolution in alkaline

The oxygen evolution reaction (OER) at the anode undergoes a sluggish multi-step process, thereby impeding overall water splitting. As the classical adsorbate evolution mechanism (AEM) involves multiple oxygen-containing intermediates, such as *OH, *O and *OOH, breaking the linear relationship of the adsorption energies between *OH and *OOH is the key to efficient oxygen evolution. Herein, we report a high-entropy FeCoNiAlZn layered double hydroxide decorated with defects (E-FeCoNiAlZn LDH) for boosting oxygen evolution in alkaline. The product exhibits high OER activity with a low overpotential of 220 at 10 mA cm−2 and outstanding stability with negligible decline after 100 h operation. The defects in E-FeCoNiAlZn LDH not only enhance the adsorption of *OH by metal sites but also foster the release of oxygen from lattice, which triggers the coupled oxygen evolution mechanism (COM). This mechanism has only *OH and *OO intermediates, perfectly avoiding the obstacles of linear relationship between *OH and *OOH. Theoretical calculations demonstrate that the introduction of defects enhances the adsorption of *OH due to the presence of unsaturated bonds. Additionally, it is evidence that the O 2p band is elevated, leading to a weakening of the metal-O bond and a reduction of the energy barrier for OO coupling.

Pyridinic N[sbnd]B pair-doped carbon microspheres with refined hierarchical architectures for rechargeable zinc-air batteries

Refined architectures are of vital importance in determining the electrocatalytic activity of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, pyridinic NB pair doped carbon microspheres (NB-CMS) with hierarchical micropore-mesopore structure are prepared via a SiO2 hard template assisted CO2 activation strategy. The pyridinic NB pair accounts for ≈ 59.9 % of all N species in NB-CMS, accelerating the ORR process with onset potential (0.996 V) and half-wave potential (0.889 V). Meanwhile, the NB-CMS also exhibits high OER performance with overpotential of 384 mV at 10 mA cm−2. The assembled Zinc-air battery exhibits maximum power density of 134 mW cm−2 and long-term charging and discharging stability over 358 h. Density functional theory (DFT) simulations reveal that the pyridinic NB pair exhibits the highest electrocatalytic performance in dual-functional catalysis, owing to the highest charge density and readily accepts electrons from *OOH adsorbate of N active site neighboring B.

NiFe layered-double-hydroxide nanosheet arrays grown in situ on Ni foam for efficient oxygen evolution reaction

Developing efficient and stable oxygen evolution reaction (OER) electrocatalysts under various alkaline conditions is crucial for commercial hydrogen (H₂) production. This study synthesized superhydrophilic NiFe LDH/NF with a nanosheet structure. The strong electronic interactions between the metals modify the electronic structures of Ni and Fe. In-situ Raman spectroscopy reveals numerous high-valent nickel intermediates with high OER activity during the reaction, significantly improving the catalyst's overall performance. At room temperature, the NiFe LDH/NF catalyst exhibits a current density of 50/100 mA cm−2 with only 217/233 mV required in 1 M KOH. Moreover, the catalyst requires only 180 mV under industrial conditions (60 °C, 6 M KOH), 243 mV in alkaline artificial seawater, and 280 mV in alkaline natural seawater to achieve 100 mA cm−2. The catalyst also exhibits long-term operational durability under these conditions, indicating a wide range of potential applications.

Selectivity Study of Direct Seawater Electrolyzer Anode Catalysts Using the Rotating Ring-Disc Electrode Method

Seawater electrolysis suffers from many issues that must be resolved before the technology can be scaled. The corrosive hypochlorite formation at the anode can damage the electrode and other electrolyzer components. Furthermore, hypochlorite is unstable and can decay, particularly when exposed to heat and metal ions, which could lead to erroneously high oxygen evolution reaction (OER) selectivity calculations in catalyst benchmarking experiments, resulting in poor catalyst and electrolyzer component selection. In this study, we used the rotating ring-disc electrode (RRDE) technique for the characterization of IrO2, NiO, Co3O4, RuO2, Pt/C, and PtRu electrocatalysts at near-neutral pH (8.4) in 0.5 M NaCl. The RRDE can overcome the challenge posed by thermocatalytic hypochlorite decay. IrO2 and PtRu were also studied over a range of chloride concentrations from 0.1 to 1 M. Our findings reveal that elevated temperatures (313 and 333 K) are conducive to higher OER selectivity, as the OER faradaic efficiency (FE) on IrO2 increased by 23% at 1.22 V vs SHE when the temperature was increased from 293 to 333 K. Increasing the chloride concentration from 0.1 to 1 M increased the OER current density by 40% and 200% on IrO2 and PtRu, respectively, indicating a synergistic relationship.

Synergistic effects of Co/Fe bimetallic polymer catalysts for enhanced ORR/OER: Insights from thermodynamic and in-situ kinetic study

Bifunctional catalysts for oxygen reduction reaction and oxygen evolution reaction in Zinc-air batteries have been long pursued for the development of clean energy transformation devices. Yet, the underlying mechanism of the promoted electrocatalytic performance is still vague. Herein, a pyrolysis-free Co/Fe bimetallic phthalocyanine coordination polymer Co/Fe-TPDA-CP is firstly synthesized using heterometal tetra-aminophthalocyanines (MTAPcs, M=Co/Fe) as structural model and N,N,N’,N’-tetra(4-folmylphenyl)-p-phenylenediamine (TPDA) as linker. The Co/Fe-TPDA-CP exhibits the high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities with low ΔE of 692 mV, superior to monometallic Fe-TPDA-CP and Co-TPDA-CP polymers. Density functional theory (DFT) calculation and thermodynamic analysis find that ORR and OER happened separately on Fe and Co sites, in which the presence of second metal modulates the d-band center and optimizes the intermediates adsorption, thereby improving the ORR/OER synergistically. Moreover, dynamic analysis explains that the enhanced ORR stability originated from the fast H2O2 decomposition catalyzed by Co-N4 sites. Furthermore, the Zn-air battery with Co/Fe-TPDA-CP electrode also exhibits a high peak power density (97 mW cm−2) and specific capacity (780 mA h g−1). Through the proof-of-concept bifunctional electrocatalyst with clear structure and synergistic mechanism, this work paves the way for future molecular oxygen electrocatalyst design.

Laser-induced graphene nano-anchored WS2/WO3 heterostructures for electrocatalytic oxygen evolution reaction

Tailoring surface components and nanostructures via integration of dual transition metal heteroatoms is a highly effective technique for the design and synthesis of electrocatalysts with superior performance. In this study, we report WS₂/WO₃ nanostructure enriched with sulphur and oxygen vacancies, embedded within laser-induced graphene (LIG) as carbon support, to improve alkaline and seawater splitting applications for the oxygen evolution reaction (OER). The LIG-WS₂/WO₃ nanohybrid demonstrates high OER activity and improved stability due to the synergistic interaction between LIG, WS₂, WO₃, and optimized proportion of sulphur and oxygen vacancies, which facilitates efficient charge transfer, reduces recombination losses and allows significant tuning of various electrocatalytic parameters as a function of annealing temperature. The optimized sample, LWSO@450, exhibits excellent electrocatalytic activity with a low overpotential of 350 mV at a current density of 50 mA/cm2 and an exceptionally low Tafel slope of 33 mV/decade in an alkaline medium. Moreover, the high electrochemically active surface area of 134 cm2, mass activity of 60 A/g, and turnover frequency of 0.012 s⁻1 indicate a substantial number of active sites. These findings highlight the considerable potential of this catalyst in various electrochemical domains, particularly in energy conversion, and other renewable energy systems, due to its cost-effectiveness, availability, and scalability.

Engineering MOF@LDH heterojunction with strong interfacial built-in electric field towards enhanced electrocatalytic water oxidation

Guiding the dynamic reconstruction of the oxygen evolution reaction (OER) is crucial for realizing the industrial application of hydrogen production through water electrolysis. In this study, we have intricately designed a built-in electric field (BIEF) between MIL-88B(Fe) and layered double hydroxide (LDH) with an adjusted work function difference. This design drives an asymmetric interfacial electron distribution, enhancing electron accumulation at the Fe sites within MIL-88B(Fe) and electron-deficient LDHs. Consequently, this setup promotes the surface dynamic reconstruction of LDHs into highly active oxyhydroxides, while simultaneously slowing down the rapid dissolution of Fe during OER operation. This optimization improves the adsorption/desorption of oxygen intermediates, ensuring a sustained high OER activity during long-term electrochemical operation. As expected, the optimal MIL-88B(Fe)@NiCo LDH configuration demonstrates a remarkably low overpotential of only 279 mV at 10 mA cm−2, maintaining operational stability for 70 h. This research significantly advances our understanding of the dynamic reconstruction of MOF@LDH heterojunctions and introduces a straightforward strategy for engineering BIEF to guide this process effectively.