Sub-2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Developing an efficient bifunctional electrocatalyst with accelerated kinetics is important but challenging for rechargeable metal-air batteries. In this study, a series of anion-regulated sub-2 nm ultrathin thiophosphate nanosheets (NiPS_3–xSe_x NSs) is rationally designed and synthesized as bifunctional oxygen evolution/reduction reaction (OER/ORR) electrocatalysts for Zn-air batteries. The increase of nominal Se dopants (0 ≤ x ≤ 0.5) leads to the expansion of (001) crystal plane spacing and partially disordered structure generation after the incorporation of Se to pristine NiPS₃. More importantly, electronic structures of active sites can be reasonably regulated via coordination of the interaction between anions and cations. Density functional theory calculations reveal that such tailored electronic structures reduce the overpotential of the thermodynamic barriers step for both OER and ORR as well as shorten energy bandgap, which can accelerate reaction kinetics in electrocatalytic processes and enhance electrical conductivity. Consequently, the obtained NiPS_3–xSe_x NSs exhibit low OER overpotential (250 mV) and positive ORR onset potential (0.94 V), large power density (152 mW cm⁻²), and robust stability (96 h cycle) for Zn-air devices, far exceeding that of precious metal catalysts. This study provides a novel tactic to design earth-abundant and highly efficient bifunctional electrocatalysts for metal-air battery technologies.     

Tuning the Electronic Bandgap of Graphdiyne by H-Substitution to Promote Interfacial Charge Carrier Separation for Enhanced Photocatalytic Hydrogen Production

Graphdiyne (GDY), which features a highly π-conjugated structure, direct bandgap, and high charge carrier mobility, presents the major requirements for photocatalysis. Up to now, all photocatalytic studies are performed without paying too much attention on the GDY bandgap (1.1 eV at the G₀W₀ many-body theory level). Such a narrow bandgap is not suitable for the band alignment between GDY and other semiconductors, making it difficult to achieve efficient photogenerated charge carrier separation. Herein, for the first time, it is demonstrated that tuning the electronic bandgap of GDY via H-substitution (H-GDY) promotes interfacial charge separation and improves photocatalytic H₂ evolution. The H-GDY exhibits an increased bandgap energy ( ≈ 2.5 eV) and exploitable conduction band minimum and valence band maximum edges. As a representative semiconductor, TiO₂ is hybridized with both H-GDY and GDY to fabricate a heterojunction. Compared to the GDY/TiO₂, the H-GDY/TiO₂ heterojunction leads to a remarkable enhancement of the photocatalytic H₂ generation by 1.35 times under UV–visible illumination (6200 µ mol h⁻¹ g⁻¹) and four times under visible light (670 µ mol h⁻¹ g⁻¹). Such enhancement is attributed to the suitable band alignment between H-GDY and TiO₂, which efficiently promotes the photogenerated electron and hole separation, as supported by density functional theory calculations.     

Lithiation-Induced Defect Engineering to Promote Oxygen Evolution Reaction

Exploring efficient electrocatalysts for oxygen evolution reaction (OER) is an urgent need to advance the development of sustainable energy conversion. Though defect engineering is considered an effective strategy to regulate catalyst activity for enhanced OER performance, the controllable synthesis of defective oxides electrocatalysts remains challenging. Here, oxygen defects are introduced into NiCo₂O₄ nanorods by an electrochemical lithiation strategy. By tuning in situ lithiation potentials, the concentration of oxygen defects and the corresponding catalytic activity can be feasibly regulated. In addition, the relationship between the changes in the defect density and electronic structure and the lithiation cut-off voltages is revealed. The results show that NiCo₂O₄ nanorods undertook intercalation and two-step conversion reaction, in which the lithiation-induced conversion reaction gives rise to a CoO@NiO-based structure with higher defect density and lower oxidation states. As a result, the defective CoO@NiO-based catalyst exhibits exceptional OER activity with an overpotential of 270 mV at 10 mA cm⁻², which is about 74 mV below the pristine nanomaterials. This research proposes a novel strategy to explore high-performance catalysts with structural stability and defect control.     

Ag Anchored Atomically Around Nanopores of Porous Co(OH)2 for Efficient Bifunctional Oxygen Catalysis

Various clean energy storage and conversion systems highly depend on rational design of efficient electrocatalysts for oxygen reactions. Increasing both gas molecular diffusion and intrinsic activity is critical to boosting its efficiency for bifunctional oxygen electrocatalysis. However, controllable synthesis of catalysts that combines gas molecular diffusion and intrinsic activity remains a fundamental challenge. Herein, a two-step synthetic strategy is adopted to fabricate a composite oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional catalyst (P-Ag-Co(OH)₂), of which, atomic Ag is anchored in reactive oxygen atoms around nanopores of Co(OH)₂ nanosheets. Abundant nanopores provide enough gas molecular diffusion channels, and the special Ag-O-Co-OH catalytic groups around nanopores display high intrinsic catalytic activity, which jointly result in an excellent ORR/OER performance. In alkaline electrolyte, P-Ag-Co(OH)₂ displays a high half-wave potential (0.902 V versus RHE) for ORR, and a low overpotential (235 mV at 10 mA cm⁻²) for OER, which is superior to non-noble catalysts in previous studies and Pt/C (Ir/C) catalyst. At the same time, the single-cell zinc-air battery is prepared with an extremely high discharge peak power density of 435 mW cm⁻² and excellent discharge–charge cycle stability.     

In Situ/Operando Capturing Unusual Ir6+ Facilitating Ultrafast Electrocatalytic Water Oxidation

Identifying real active sites and understanding the mechanism of oxygen evolution reaction (OER) are still a big challenge today for developing efficient electrochemical catalysts in renewable energy technologies. Here, using a combined in situ/operando experiments and theory, the catalytic mechanism of the ordered OER active Co and Ir ions in Sr₂CoIrO_6−δ is studied, which exhibits an unprecedented low overpotential 210 mV to achieve 10 mA cm^–2, ranking the highest performance among perovskite-based solid-state catalysts. Operando X-ray absorption spectroscopies as a function of applied voltage indicates that Ir⁴⁺ ion is gradually converted into extremely high-valence Ir^5+/6+, while the part of Co³⁺ ion is transferred into Co⁴⁺ under OER process. Density functional theory calculations explicitly reveal the order Co-O-Ir network as an origin of ultrahigh OER activity. The work opens a promising path to overcome the sluggish kinetics of OER bottleneck for water splitting via proper arrangements of the multi-active sites in catalyst.     

Dual Active Sites Engineering on Sea Urchin-Like CoNiS Hollow Nanosphere for Stabilizing Oxygen Electrocatalysis via a Template-Free Vulcanization Strategy

Manipulating electronic structure and defects is crucial to achieve on-demand functionalities of bimetallic sulfide catalysts for oxygen reduction/evolution reactions (ORR/OER). Here, via a vulcanization strategy, defects-abundant NiCo₂S₄ needles obtained from sea urchin-like NiCo₂O₄ are anchored on surface of hollow carbon-sphere (NiCo₂S₄/HCS). NiCo₂S₄ nanoneedles (≈7.5 nm) are radially grown on shell of HCS with a cavity (254.5 m² g⁻¹), and their surface becomes rougher after vulcanization due to anion exchange reaction. As-marked NiCo₂S₄/HCS-3 exhibits better ORR activity (half-wave potential of 0.89 V) and methanol tolerance than Pt/C (0.86 V). NiCo₂S₄/HCS-3 shows a lower OER overpotential (310 mV) than RuO₂ and retains 90.9% of initial activity after 9 h. Notably, zinc–air battery with NiCo₂S₄/HCS-3 reveals highly-stable charging/discharging voltages of 2.11/1.16 V with a negligible fading for 200 h. NiCo₂S₄ grown on outer/inner surfaces of HCS expands spatial distribution of active sites to enhance reactants-electrode contact and charge transfer. Theoretical calculation shows that Co-site with an electronic state near Fermi energy level is chiefly-responsible for ORR, while Ni-site mainly affords high OER activity. Bader charge analyses reveal that S doping increases the charge density and redox active sites in NiCo₂S₄. It sheds light on the understanding of electrocatalytic mechanisms on bimetallic sulfides for electronic device.     

Sub-2 nm Ultrathin and Robust 2D FeNi Layered Double Hydroxide Nanosheets Packed with 1D FeNi-MOFs for Enhanced Oxygen Evolution Electrocatalysis

Water oxidation is a critical process for electrochemical water splitting due to its inherent sluggish kinetics. In spite of the high catalytic activities of noble metal-based electrocatalysts for water oxidation, their high cost, rare reserves, and low stabilities drive researchers to exploit efficient but low-cost electrocatalysts. Ultrathin 2D nanomaterials are considered efficient electrocatalysts for oxygen evolution reaction (OER) in water splitting. Herein, a facile strategy is proposed to fabricate 2D FeNi layered double hydroxide (FeNi-LDH) nanosheets packed with the in situ produced 1D sword-like FeNi-MOFs by using FeNi-LDH as a semi-sacrificial template. In the composite, the thickness of the formed nanosheets is only 1.34 nm, much thinner than that of most previously reported 2D materials. The 1D porous sword-like MOF nanorods have a long length of around 1.3 µm. Due to the unique 2D/1D combined structure, the as-prepared FeNi LDH/MOF is directly used as electrocatalyst for the OER displays enhanced OER electrocatalytic performance with a low overpotential of 272 mV@100 mA cm^–2, a small Tafel slope of 34.1 mV dec^–1, high long-term durability. This work provides a new way to fabricate integrated ultrathin 2D nanosheets and MOFs as advanced catalysts for electrochemical energy conversion.     

Mechanochemical Post-Synthesis of Metal–Organic Framework-Based Pre-Electrocatalysts with Surface Fe?O?Ni/Co Bonding for Highly Efficient Oxygen Evolution

Rational surface engineering of metal–organic frameworks (MOFs) provide potential opportunities to address the sluggish kinetics of oxygen evolution reaction (OER). However, the development of MOF-based materials with low overpotentials remains a great challenge. Herein, a post-synthesis strategy to prepare highly efficient MOF-based pre-electrocatalysts via all-solid-phase mechanochemistry is demonstrated. The surface of a Fe-based MOF (MIL-53) can be reconstructed and anchored with atomically dispersed Ni/Co sites. As expected, the optimized M-NiA-CoN exhibits a very low overpotential of 180 mV at 10 mA cm⁻² and a small Tafel slope of 41 mV dec⁻¹ in 1 m KOH electrolyte. The superior electrocatalytic OER activity is mainly due to the formation of surface Fe O Ni/Co bonding. Furthermore, density functional theory calculations reveal that the transformation from ^*OH to ^*O is the rate-determining step and the electrocatalytic OER activity trend at different metal sites is Co > Ni≈Fe.     

A Kinetic Control Strategy for One-Pot Synthesis of Efficient Bimetallic Metal-Organic Framework/Layered Double Hydroxide Heterojunction Oxygen Evolution Electrocatalysts

Heterojunction materials are promising candidates for oxygen evolution reaction (OER) electrocatalysts to break the linear scaling relationship and lower the reaction barrier. However, the application of heterojunction materials is always hindered by the complicated multistep synthetic procedures which bring cost, complexity, and reproducibility issues. Herein, a strategy of kinetic controlled synthesis is developed to achieve the one-pot formation of bimetallic metal-organic framework (MOF)/layered double hydroxide (LDH) heterojunction electrodes as highly efficient OER electrocatalysts. The heterojunction electrodes present hierarchical structures with highly porous NiFe-LDH nanosheet networks vertically grown on the surface of NiFe-MOF-74 microprisms, promoting fast mass transport and high exposure of active sites. The strong interactions at the MOF/LDH heterojunction interfaces contribute to the outstanding OER activity surpassing the state-of-art RuO₂ OER catalysts. The MOF/LDH heterojunction electrode exhibits an ultralow overpotential of only 159.7 mV to reach the current density of 10 mA cm⁻², and yields large current densities at small overpotential (100 mA cm⁻² at 230.2 mV and 1000 mA cm⁻² at 284.3 mV) with long-term durability. This study presents an innovative approach to construct heterojunction materials with simple one-step synthesis, offering a promising pathway for high-efficiency electrocatalyst development.     

Non-Volatile Electrolyte-Gated Transistors Based on Graphdiyne/MoS2 with Robust Stability for Low-Power Neuromorphic Computing and Logic-In-Memory

Artificial synapses are the key building blocks for low-power neuromorphic computing that can go beyond the constraints of von Neumann architecture. In comparison with two-terminal memristors and three-terminal transistors with filament-formation and charge-trapping mechanisms, emerging electrolyte-gated transistors (EGTs) have been demonstrated as a promising candidate for neuromorphic applications due to their prominent analog switching performance. Here, a novel graphdiyne (GDY)/MoS₂-based EGT is proposed, where an ion-storage layer (GDY) is adopted to EGTs for the first time. Benefitting from this Li-ion-storage layer, the GDY/MoS₂-based EGT features a robust stability (variation < 1% for over 2000 cycles), an ultralow energy consumption (50 aJ µm⁻²), and long retention characteristics (>10⁴ s). In addition, a quasi-linear conductance update with low noise (1.3%), an ultrahigh G_max/G_min ratio (10³), and an ultralow readout conductance (<10 nS) have been demonstrated by this device, enabling the implementation of the neuromorphic computing with near-ideal accuracies. Moreover, the non-volatile characteristics of the GDY/MoS₂-based EGT enable it to demonstrate logic-in-memory functions, which can execute logic processing and store logic results in a single device. These results highlight the potential of the GDY/MoS₂-based EGT for next-generation low-power electronics beyond von Neumann architecture.     

In Situ Reconstruction of V-Doped Ni2P Pre-Catalysts with Tunable Electronic Structures for Water Oxidation

Nickel-based electrocatalysts are promising candidates for oxygen evolution reaction (OER) but suffer from high activation overpotentials. Herein, in situ structural reconstruction of V-doped Ni₂P pre-catalyst to form highly active NiV oxyhydroxides for OER is reported, during which the partial dissolution of V creates a disordered Ni structure with an enlarged electrochemical surface area. Operando electrochemical impedance spectroscopy reveals that the synergistic interaction between the Ni hosts and the remaining V dopants can regulate the electronic structure of NiV oxyhydroxides, which leads to enhanced kinetics for the adsorption of *OH and deprotonation of *OOH intermediates. Raman spectroscopy and X-ray absorption spectroscopy further demonstrate that the increased content of active β-NiOOH phase with the disordered Ni active sites contributes to OER activity enhancement. Density functional theory calculations verify that the V dopants facilitate the generation of *O intermediates during OER, which is the rate-determining step for realizing efficient O₂ evolution. Optimization of these properties endows the NiV oxyhydroxide electrode with a low overpotential of 221 mV to deliver a current density of 10 mA cm⁻² and excellent stability in the alkaline electrolyte.     

Etching‐Doping Sedimentation Equilibrium Strategy: Accelerating Kinetics on Hollow Rh‐Doped CoFe‐Layered Double Hydroxides for Water Splitting

Exploring highly active and inexpensive bifunctional electrocatalysts for water‐splitting is considered to be one of the prerequisites for developing hydrogen energy technology. Here, an efficient simultaneous etching‐doping sedimentation equilibrium (EDSE) strategy is proposed to design and prepare hollow Rh‐doped CoFe‐layered double hydroxides for overall water splitting. The elaborate electrocatalyst with optimized composition and typical hollow structure accelerates the electrochemical reactions, which can achieve a current density of 10 mA cm^?2 at an overpotential of 28 mV (600 mA cm^?2 at 188 mV) for hydrogen evolution reaction (HER) and 100 mA cm^?2 at 245 mV for oxygen evolution reaction (OER). The cell voltage for overall water splitting of the electrolyzer assembled by this electrocatalyst is only 1.46 V, a value far lower than that of commercial electrolyzer constructed by Pt/C and RuO₂ and most reported bifunctional electrocatalysts. Furthermore, the existence of Fe vacancies introduced by Rh doping and the typical hollow structure are demonstrated to optimize the entire HER and OER processes. EDSE associates doping with template‐directed hollow structures and paves a new avenue for developing bifunctional electrocatalysts for overall water splitting. It is also believed to be practical in other catalysis fields as well.     

Dual-Sites Coordination Engineering of Single Atom Catalysts for Full-Temperature Adaptive Flexible Ultralong-Life Solid-State Zn−Air Batteries

High-performance rechargeable Zn-air batteries with long-life stability are desirable for power applications in electric vehicles. The key component of the Zn-air batteries is the bifunctional oxygen electrocatalyst, however, designing a bifunctional oxygen electrocatalyst with high intrinsic reversibility and durability is a challenge. Through density functional theory calculations, it is found that the catalytic activity originated from the electronic and geometric coordination structures synergistic effect of the Fe and Co dual-sites with metal-N₄ coordination environment, assisting the stronger hybridization of electronic orbitals between Co (dxz, dz²) and OO* (px, pz), thus making the stronger O₂ active ability of Co active site. These findings enable to development of a fancy dual single-atom catalyst comprising adjacent Fe N₄ and Co N₄ sites on N-doped carbon matrix (FeCo-NC). FeCo-NC exhibits extraordinary bifunctional activities for oxygen reduction and evolution reaction (ORR/OER), which displays high half-wave potential (0.893 V) for the ORR, and low overpotential (343 mV) at 10 mA cm⁻² for the OER. The assembled FeCo-NC air-electrode works well in the flexible solid-state Zn-air battery with a high specific capacity of 747.0 mAh g⁻¹, a long-time stability of more than 400 h (30 °C), and also a superior performance at extreme temperatures (−30 °C–60 °C).     

Optimizing the Electronic Structure of Ruthenium Oxide by Neodymium Doping for Enhanced Acidic Oxygen Evolution Catalysis

It is a great challenge to design active and durable oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) electrolyzer due to the high dissolution of electrocatalysts in acidic solution. Herein, the Nd-doped RuO₂ (Nd_0.1RuO_x) is developed for enhanced oxygen evolution in 0.5 m H₂SO₄ solution with an overpotential of 211 mV to achieve 10 mA cm⁻². The theoretical calculation reveals that the improved activity of Nd_0.1RuO_x is due to the moderate decrease of d-band center energy, which balances the adsorption and desorption of oxygen intermediates. Moreover, the formation of more high valence state Ru⁴⁺ in Nd_0.1RuO_x is beneficial to the chemical stability of Ru species during the OER process, indicating that the introduction of Nd can effectively suppress the dissolution of Ru in acidic electrolytes. In addition, the PEM electrolyzer using Nd_0.1RuO_x/CC as the anode can be operated at 10 mA cm⁻² stably for 50 h. This study sheds new light on the design of the OER catalysts in acid by engineering the electronic structure of RuO₂.     

The Guest Doping Effects of Fe on Bimetallic NiCo Layered Double Hydroxide for Enhanced Electrochemical Oxygen Evolution Reaction: Theoretical Screening and Experimental Verification

Exploring efficient transition-metal-based electrocatalysts for oxygen evolution reaction (OER) is imperative but remain challenging for sustainable energy storage and conversion systems. Foreign species doping is a significant regulation strategy to enhance the intrinsic activity of host matrix. However, the potential relationship of structure-activity caused by guest doping elements is seldom tracked systematically. In this case, both theoretical screening and experimental verification are complementarily employed to investigate the guest doping effects of ten first-row transition metals (Sc∼Zn) on bimetallic NiCo layered double hydroxide (NiCo-LDH). As a result, the optimized Fe-doped NiCo-LDH is identified as the most promising candidate toward alkaline electrocatalytic OER, which exhibits the quasi-industrial current density of 1000 mA cm⁻² at overpotential of 400 mV. Meanwhile, it also shows impressively long-term stability of 500 h at 500 mA cm⁻² with a negligible activity loss. Moreover, in situ electrochemical Raman spectroscopy unveils the dynamic structure evolution from pre-catalytic state (Fe-NiCo-LDH) to metal oxyhydroxide (Fe-(NiCo)OOH) during the oxidation reaction, and ab-initio molecular dynamics simulations are further performed to confirm the thermodynamic stability of activated Fe-(NiCo)OOH phase. This work provides a promising platform for exploring the critical role of transition metal guest doping on host matrix in developing industrially required OER electrocatalysts.     

Regulating the Electronic Structure of CoP Nanosheets by O Incorporation for High‐Efficiency Electrochemical Overall Water Splitting

The exploration of earth‐abundant and high‐efficiency bifunctional electrocatalysts for overall water splitting is of vital importance for the future of the hydrogen economy. Regulation of electronic structure through heteroatom doping represents one of the most powerful strategies to boost the electrocatalytic performance of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a rational design of O‐incorporated CoP (denoted as O‐CoP) nanosheets, which synergistically integrate the favorable thermodynamics through modification of electronic structures with accelerated kinetics through nanostructuring, is reported. Experimental results and density functional theory simulations manifest that the appropriate O incorporation into CoP can dramatically modulate the electronic structure of CoP and alter the adsorption free energies of reaction intermediates, thus promoting the HER and OER activities. Specifically, the optimized O‐CoP nanosheets exhibit efficient bifunctional performance in alkaline electrolyte, requiring overpotentials of 98 and 310 mV to deliver a current density of 10 mA cm^?2 for HER and OER, respectively. When served as bifunctional electrocatalysts for overall water splitting, a low cell voltage of 1.60 V is needed for achieving a current density of 10 mA cm^?2. This proposed anion‐doping strategy will bring new inspiration to boost the electrocatalytic performance of transition metal–based electrocatalysts for energy conversion applications.     

A CoN-based OER Electrocatalyst Capable in Neutral Medium: Atomic Layer Deposition as Rational Strategy for Fabrication

Reported herein is an active and durable CoN-containing oxygen evolution reaction (OER) electrocatalyst which efficiently functions in a neutral medium (pH ≈7). The composite material (N, S)-RGO@CoN is synthesized by delicate atomic layer deposition (ALD) of CoN on a nitrogen and sulfur (N, S) co-doped reduced graphene oxide (RGO) substrate. Representative results of the comprehensive study are: 1) The flower-like sphere RGO substrate prepared by spray drying method features rich physical and chemical properties, which are beneficial for rapid mass/charge transfer to improve the intrinsic OER process; 2) the optimal ALD material for OER tests is afforded by tuning spray conditions and ALD parameters. Versatile structural and compositional characterizations confirm uniform growth and strong chemical coupling of nanostructured CoN on (N, S)-RGO matrix; 3) the material is electrocatalytically active and durable in a neutral electrolyte, recording an OER overpotential of 220 mV at a current density of 10 mA cm⁻² and stability of 20 h continuous catalysis at 20 mA cm⁻² with nearly 100% Faradic efficiency; 4) Upon the experimental studies and density functional theory calculations, the eventual mechanism of remarkable OER activity conforms to the structural fate of ALD CoN electronic coupling to the carbon substrate.     

Linker Defects in Metal–Organic Frameworks for the Construction of Interfacial Dual Metal Sites with High Oxygen Evolution Activity

Designing efficient electrocatalysts based on metal–organic framework (MOF) nanosheet arrays (MOFNAs) with controlled active heterointerface for the oxygen evolution reaction (OER) is greatly desired yet challenging. Herein, a facile strategy for the synthesis of MOF-based nanosheet arrays (γ-FeOOH/Ni-MOFNA) is developed with abundant heterointerfaces between Ni-MOF and γ-FeOOH nanosheets by introducing linker defects to the former. The experimental and theoretical results show the key role of linker defects in inducing the growth of secondary γ-FeOOH nanosheets onto the surface of Ni-MOFNAs, which further leads to the formation of interfacial Ni/Fe dual sites with high oxygen evolution activity. Notably, the resulting γ-FeOOH/Ni-MOFNA exhibits excellent OER performance with low overpotentials of 193 and 222 mV at 10 and 100 mA cm⁻², respectively. Furthermore, the study of the structure–performance relationship of MOF-based heterostructures reveals that Ni sites at the interface of the γ-FeOOH/Ni-MOFNA have higher activity than those at the interface of NiFe layered double hydroxide and Ni-MOFNA. This study provides a new prospect on heterostructured electrocatalysts with highly active sites for enhanced OER.     

Efficient Optimization of Electron/Oxygen Pathway by Constructing Ceria/Hydroxide Interface for Highly Active Oxygen Evolution Reaction

Owing to the unique electronic properties, rare‐earth modulations in noble‐metal electrocatalysts emerge as a critical strategy for a broad range of renewable energy solutions such as water‐splitting and metal–air batteries. Beyond the typical doping strategy that suffers from synthesis difficulties and concentration limitations, the innovative introduction of rare‐earth is highly desired. Herein, a novel synthesis strategy is presented by introducing CeO₂ support for the nickel–iron–chromium hydroxide (NFC) to boost the oxygen evolution reaction (OER) performance, which achieves an ultralow overpotential at 10 mA cm^?2 of 230.8 mV, the Tafel slope of 32.7 mV dec^?1, as well as the excellent durability in alkaline solution. Density functional theory calculations prove the established d–f electronic ladders, by the interaction between NFC and CeO₂, evidently boosts the high‐speed electron transfer. Meanwhile, the stable valence state in CeO₂ preserves the high electronic reactivity for OER. This work demonstrates a promising approach in fabricating a nonprecious OER electrocatalyst with the facilitation of rare‐earth oxides to reach both excellent activity and high stability.