Iron Oxyhydroxide: Structure and Applications in Electrocatalytic Oxygen Evolution Reaction

Oxygen evolution reaction (OER) is the anodic half-reaction for crucial energy devices, such as water electrolysis, metal–air battery, and electrochemical CO₂ reduction. Fe-based materials are recognized as one of the most promising electrocatalysts for OER because of its extremely low price and high activity. In particular, iron oxyhydroxide (FeOOH) is not only highly active toward OER, but also widely accepted as the true active species of Fe-based OER electrocatalysts for plenty of Fe-based materials are converted into FeOOH during OER test. Herein, the recent advances of FeOOH-based nano-structure and its application in OER are reviewed. The relationship between FeOOH structure and its catalytic performance, followed by the introduction of current strategies for enhancing the OER activity (i.e., crystalline phase engineering, element doping, and construction of hybrid materials) is mainly focused. Finally, a summary and perspective about the remaining challenges and future opportunities in this area and further the design of Fe-based OER electrocatalysts are provided.     

Hierarchical Porous NC@CuCo Nitride Nanosheet Networks: Highly Efficient Bifunctional Electrocatalyst for Overall Water Splitting and Selective Electrooxidation of Benzyl Alcohol

Highly active and stable bifunctional electrocatalysts for overall water splitting are important for clean and renewable energy technologies. The development of energy‐saving electrocatalysts for hydrogen evolution reaction (HER) by replacing the sluggish oxygen evolution reaction (OER) with a thermodynamically favorable electrochemical oxidation (ECO) reaction has attracted increasing attention. In this study, a self‐supported, hierarchical, porous, nitrogen‐doped carbon (NC)@CuCo₂N_x/carbon fiber (CF) is fabricated and used as an efficient bifunctional electrocatalyst for both HER and OER in alkaline solutions with excellent activity and stability. Moreover, a two‐electrode electrolyzer is assembled using the NC@CuCo₂N_x/CF as an electrocatalyst at both cathode and anode electrodes for H₂ production and selective ECO of benzyl alcohol with high conversion and selectivity. The excellent electrocatalytic activity is proposed to be mainly due to the hierarchical architecture beneficial for exposing more catalytic active sites, enhancing mass transport. Density functional theoretical calculations reveal that the adsorption energies of key species can be modulated due to the synergistic effect between CoN and CuN. This work provides a reference for the development of high‐performance bifunctional electrocatalysts for simultaneous production of H₂ and high‐value‐added fine chemicals.     

Recent Advances in Non‐Noble Bifunctional Oxygen Electrocatalysts toward Large‐Scale Production

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial reactions in energy conversion and storage systems including fuel cells, metal–air batteries, and electrolyzers. Developing low‐cost, high‐efficiency, and durable non‐noble bifunctional oxygen electrocatalysts is the key to the commercialization of these devices. Here, based on an in‐depth understanding of ORR/OER reaction mechanisms, recent advances in the development of non‐noble electrocatalysts for ORR/OER are reviewed. In particular, rational design for enhancing the activity and stability and scalable synthesis toward the large‐scale production of bifunctional electrocatalysts are highlighted. Prospects and future challenges in the field of oxygen electrocatalysis are presented.     

Advances in Manganese‐Based Oxides Cathodic Electrocatalysts for Li–Air Batteries

Li–air batteries, characteristic of superhigh theoretical specific energy density, cost‐efficiency, and environment‐friendly merits, have aroused ever‐increasing attention. Nevertheless, relatively low Coulomb efficiency, severe potential hysteresis, and poor rate capability, which mainly result from sluggish oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) kinetics, as well as pitiful cycle stability caused by parasitic reactions, extremely limit their practical applications. Manganese (Mn)‐based oxides and their composites can exhibit high ORR and OER activities, reduce charge/discharge overpotential, and improve the cycling stability when used as cathodic catalyst materials. Herein, energy storage mechanisms for Li–air batteries are summarized, followed by a systematic overview of the progress of manganese‐based oxides (MnO₂ with different crystal structures, MnO, MnOOH, Mn₂O₃, Mn₃O₄, MnOx, perovskite‐type and spinel‐type manganese oxides, etc.) cathodic materials for Li–air batteries in the recent years. The focus lies on the effects of crystal structure, design strategy, chemical composition, and microscopic physical parameters on ORR and OER activities of various Mn‐based oxides, and even the overall performance of Li–air batteries. Finally, a prospect of the research for Mn‐based oxides cathodic catalysts in the future is made, and some new insights for more reasonable design of Mn‐based oxides electrocatalysts with higher catalytic efficiency are provided.     

Facile Synthesis of Medium-Entropy Metal Sulfides as High-Efficiency Electrocatalysts toward Oxygen Evolution Reaction

Developing highly efficient and durable electrocatalysts toward oxygen evolution reaction (OER) is an urgent demand to produce clean hydrogen energy. In this study, a series of medium-entropy metal sulfides (MEMS) of (NiFeCoX)₃S₄ (where X = Mn, Cr, Zn) are synthesized by a facile one-pot solvothermal strategy using molecular precursors. Benefiting from the multiple-metal synergistic effect and the low crystallinity, these MEMS show significantly enhanced electrocatalytic OER activity compared with the binary-metal (NiFe)₃S₄ and ternary-metal (NiFeCo)₃S₄ counterparts. Especially, (NiFeCoMn)₃S₄ delivers a low overpotential of 289 mV at 10 mA cm⁻², a decent Tafel slope of 75.6 mV dec⁻¹ and robust catalytic stability in alkaline medium, outperforming the costly IrO₂ benchmark electrocatalyst and the majority of the reported metal sulfide-based electrocatalysts until now. These MEMS with facile synthesis and excellent electrocatalytic performance bring a great opportunity to design desirable electrocatalysts for practical application.     

Metal–Organic Frameworks Derived Interconnected Bimetallic Metaphosphate Nanoarrays for Efficient Electrocatalytic Oxygen Evolution

The development of low‐cost, high‐performance, and stable electrocatalysts for the sluggish oxygen evolution reaction (OER) in water splitting is essential for renewable and clean energy technologies. Herein, the interconnected nanoarrays consisting of Co–Ni bimetallic metaphosphate nanoparticles embedded in a carbon matrix (Co_2?xNi_xP₄O₁₂‐C) are fabricated through a mild phosphorylating process of cobalt–nickel zeolitic imidazolate frameworks (CoNi‐ZIF). Density functional theory calculations reveal moderate adsorption of oxygenated intermediates on the doping Ni site, and current density simulations imply homogeneous and higher current density due to the morphology integrity of the interconnected metaphosphate nanoarrays. As a consequence, the optimized Co_1.6Ni_0.4P₄O₁₂‐C affords a superior OER activity (η = 230 mV at 10 mA cm^?2) and long‐term stability in alkaline media (1 m KOH) that are comparable to most reported catalysts. The strategy for balancing the doping effect and morphology effect provides a new perspective when designing and developing highly efficient electrocatalysts for energy conversion and storage applications.     

Fe3O4‐Decorated Co9S8 Nanoparticles In Situ Grown on Reduced Graphene Oxide: A New and Efficient Electrocatalyst for Oxygen Evolution Reaction

Cobalt sulfide materials have attracted enormous interest as low‐cost alternatives to noble‐metal catalysts capable of catalyzing both oxygen reduction and oxygen evolution reactions. Although recent advances have been achieved in the development of various cobalt sulfide composites to expedite their oxygen reduction reaction properties, to improve their poor oxygen evolution reaction (OER) activity is still challenging, which significantly limits their utilization. Here, the synthesis of Fe₃O₄‐decorated Co₉S₈ nanoparticles in situ grown on a reduced graphene oxide surface (Fe₃O₄@Co₉S₈/rGO) and the use of it as a remarkably active and stable OER catalyst are first reported. Loading of Fe₃O₄ on cobalt sulfide induces the formation of pure phase Co₉S₈ and highly improves the catalytic activity for OER. The composite exhibits superior OER performance with a small overpotential of 0.34 V at the current density of 10 mA cm^?2 and high stability. It is believed that the electron transfer trend from Fe species to Co₉S₈ promotes the breaking of the Co–O bond in the stable configuration (Co–O–O superoxo group), attributing to the excellent catalytic activity. This development offers a new and effective cobalt sulfide‐based oxygen evolution electrocatalysts to replace the expensive commercial catalysts such as RuO₂ or IrO₂.     

Cobalt−Iron Oxide Nanosheets for High‐Efficiency Solar‐Driven CO2−H2O Coupling Electrocatalytic Reactions

Solar‐driven electrochemical overall CO₂ splitting (OCO₂S) offers a promising route to store sustainable energy; however, its extensive implementation is hindered by the sluggish kinetics of two key reactions (i.e., CO₂ reduction reaction and oxygen evolution reaction (CO₂RR and OER, respectively)). Here, as dual‐functional catalysts, Co₂FeO₄ nanosheet arrays having high electrocatalytic activities toward CO₂RR and OER are developed. When the catalyst is applied to a complete OCO₂S system driven by a triple junction GaInP₂/GaAs/Ge photovoltaic cell, it shows a high photocurrent density of ≈13.1 mA cm^?2, corresponding to a remarkably high solar‐to‐CO efficiency of 15.5%. Density functional theory studies suggest that the Co sites in Co₂FeO₄ are favorable to the formation of *COOH and *O intermediates and thus account for its efficient bifunctional activities. The results will facilitate future studies for designing highly effective electrocatalysts and devices for OCO₂S.     

Electronic and Vacancy Engineering of Mo–RuCoOx Nanoarrays for High-Efficiency Water Splitting (Adv. Funct. Mater. 40/2023)

Exploring efficient strategies to achieve novel high-efficiency catalysts for water splitting is of great significance to develop hydrogen energy technology. Herein, unique molybdenum (Mo)-doped ruthenium–cobalt oxide (Mo–RuCoO_x) nanosheet arrays are prepared as a high-performance bifunctional electrocatalyst toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) through combining electronic and vacancy engineering. Theoretical calculations and experimental results reveal that the incorporation of Ru and Mo can effectively tune the electronic structure, and the controllable Mo dissolution coupling with the oxygen vacancy generation during surface reconstruction is able to optimize the adsorption energy of hydrogen/oxygen intermediates, thus greatly accelerating the kinetics for both HER and OER. As a result, the Mo–RuCoO_x nanoarrays exhibit remarkably low overpotentials of 41 and 156 mV at 10 mA cm⁻² for HER and OER in 1 m KOH, respectively. Furthermore, the two-electrode electrolyzer assembled by the Mo–RuCoO_x nanoarrays requires a cell voltage as low as 1.457 V to achieve 10 mA cm⁻² for alkaline overall water splitting. This work holds great promise to develop novel and highly active electrocatalysts for future energy conversion applications.     

Promoting Active Sites in Core–Shell Nanowire Array as Mott–Schottky Electrocatalysts for Efficient and Stable Overall Water Splitting

Developing earth‐abundant, active, and robust electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a vital challenge for efficient conversion of sustainable energy sources. Herein, metal–semiconductor hybrids are reported with metallic nanoalloys on various defective oxide nanowire arrays (Cu/CuO_x, Co/CoO_x, and CuCo/CuCoO_x) as typical Mott–Schottky electrocatalysts. To build the highway of continuous electron transport between metals and semiconductors, nitrogen‐doped carbon (NC) has been implanted on metal–semiconductor nanowire array as core–shell conductive architecture. As expected, NC/CuCo/CuCoO_x nanowires arrays, as integrated Mott–Schottky electrocatalysts, present an overpotential of 112 mV at 10 mA cm^?2 and a low Tafel slope of 55 mV dec^?1 for HER, simultaneously delivering an overpotential of 190 mV at 10 mA cm^?2 for OER. Most importantly, NC/CuCo/CuCoO_x architectures, as both the anode and the cathode for overall water splitting, exhibit a current density of 10 mA cm^?2 at a cell voltage of 1.53 V with excellent stability due to high conductivity, large active surface area, abundant active sites, and the continuous electron transport from prominent synergetic effect among metal, semiconductor, and nitrogen‐doped carbon. This work represents an avenue to design and develop efficient and stable Mott–Schottky bifunctional electrocatalysts for promising energy conversion.     

Physically Adsorbed Metal Ions in Porous Supports as Electrocatalysts for Oxygen Evolution Reaction

Developing highly efficient and earth‐abundant electrocatalysts for the oxygen evolution reaction (OER) is significantly important for water‐splitting. Here, for the first time it is reported that the physically adsorbed metal ions (PAMI) in porous materials can be served as highly efficient OER electrocatalysts, which provides a universal PAMI method to develop electrocatalysts. This PAMI method can be applied to almost all porous supports, including graphene, carbon nanotubes, C₃N₄, CaCO₃, and porous organic polymers and all the systems exhibit excellent OER performance. In particular, the as‐synthesized Co_0.7Fe_0.3CB exhibits a small overpotential of 295 mV and 350 mV at the current density of 10 mA cm^?2 and 100 mA cm^?2, respectively, which exceeds commercial 40 wt% IrO₂/CB and most reported non‐noble metal‐based OER catalysts. Moreover, the mass activity of Co_0.7Fe_0.3CB reaches 643.4 A g^?1 at the overpotential of 320 mV, which is nearly 4.7 times higher than that of 40 wt% IrO₂/CB. In addition, the advanced ex situ and in situ synchrotron X‐ray characterizations are carried out to unravel the PAMI synthetic process. In short, this PAMI method will break the conversional understanding, i.e., the most OER catalysts are synthesized chemically, because the new PAMI method does not require any chemical synthesis, which therefore opens a new avenue for the development of OER electrocatalysts.     

Leaf-Structure-Inspired Through-Hole Electrode with Boosted Mass Transfer and Photothermal Effect for Oxygen Evolution Reactions

The sluggish kinetics of oxygen evolution reaction (OER) remains a bottleneck for the electrocatalytic water splitting. In addition to improving the intrinsic activity of electrocatalysts, the electrode structure and external environment also have a significant influence on catalytic performance. Inspired by photosynthesis in plant leaves, a photothermal conversion strategy is proposed via the decoration of photothermal responsive MoS₂/FeCoNiS-nanotube (MoS₂/FeCoNiS-NT) on designed through-hole porous nickel foam (PNF), defined as MoS₂/FeCoNiS-NT@PNF, to boost OER performance. The PNF facilitated bubble transport in OER by mimicking stomata structure of the leaf, and simultaneously, the MoS₂/FeCoNiS-NT increases light absorption and photothermal conversion by simulating the leaf epidermis. Benefiting from bionic structure and functional design, the MoS₂/FeCoNiS-NT@PNF electrode exhibits highly effective oxygen-evolving ability and excellent photothermal conversion capacity (surface temperature: 25 °C → 52.3 °C, AM1.5G), which increases the intrinsic activity of electrocatalysts. With the assistance of optimized electrode structure and the photothermal effect, the MoS₂/FeCoNiS-NT@PNF electrode exhibits a low overpotential of 214 mV to achieve 50 mA cm⁻². This research reveals that tuning the electrode structure can promote light absorption in the electrolyte in favor of OER performance, which can serve as an inspiration for the development of high-performance catalytic electrodes.     

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.     

Fe3C‐Co Nanoparticles Encapsulated in a Hierarchical Structure of N‐Doped Carbon as a Multifunctional Electrocatalyst for ORR,OER, and HER

Rational design of non‐noble metal catalysts with robust and durable electrocatalytic activity for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is extremely important for renewable energy conversion and storage, regenerative fuel cells, rechargeable metal–air batteries, water splitting etc. In this work, a unique hybrid material consisting of Fe₃C and Co nanoparticles encapsulated in a nanoporous hierarchical structure of N‐doped carbon (Fe₃C‐Co/NC) is fabricated for the first time via a facile template‐removal method. Such an ingenious structure shows great features: the marriage of 1D carbon nanotubes and 2D carbon nanosheets, abundant active sites resulting from various active species of Fe₃C, Co, and NC, mesoporous carbon structure, and intimate integration among Fe₃C, Co, and NC. As a multifunctional electrocatalyst, the Fe₃C‐Co/NC hybrid exhibits excellent performance for ORR, OER, and HER, outperforming most of reported triple functional electrocatalysts. This study provides a new perspective to construct multifunctional catalysts with well‐designed structure and superior performance for clean energy conversion technologies.     

Tuning Bifunctional Oxygen Electrocatalysts by Changing the A‐Site Rare‐Earth Element in Perovskite Nickelates

Perovskite‐structured (ABO₃) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, a set of epitaxial rare‐earth nickelates (RNiO₃) thin films is investigated with controlled A‐site isovalent substitution to correlate their structure and physical properties with ORR/OER activities, examined by using a three‐electrode system in O₂‐saturated 0.1 m KOH electrolyte. The ORR activity decreases monotonically with decreasing the A‐site element ionic radius which lowers the conductivity of RNiO₃ (R = La, La_0.5Nd_0.5, La_0.2Nd_0.8, Nd, Nd_0.5Sm_0.5, Sm, and Gd) films, with LaNiO₃ being the most conductive and active. On the other hand, the OER activity initially increases upon substituting La with Nd and is maximal at La_0.2Nd_0.8NiO₃. Moreover, the OER activity remains comparable within error through Sm‐doped NdNiO₃. Beyond that, the activity cannot be measured due to the potential voltage drop across the film. The improved OER activity is ascribed to the partial reduction of Ni³⁺ to Ni²⁺ as a result of oxygen vacancies, which increases the average occupancy of the e_g antibonding orbital to more than one. The work highlights the importance of tuning A‐site elements as an effective strategy for balancing ORR and OER activities of bifunctional electrocatalysts.     

Ultrathin IrO2 Nanoneedles for Electrochemical Water Oxidation

Electrochemical water splitting is promising for utilizing intermittent renewable energy. The sluggish kinetics of the oxygen evolution reaction (OER), however, is a bottleneck in obtaining high efficiency. Only a few OER electrocatalysts have been developed for the use in acidic media despite the importance of a proton exchange membrane (PEM) water electrolyzer. IrO₂ is the only material that is both active and stable for the OER in highly corrosive acidic conditions. Herein, a facile and scalable synthesis of ultrathin IrO₂ nanoneedles is reported with a diameter of 2 nm using a modified molten salt method. The activity and durability for the OER are significantly enhanced on the ultrathin IrO₂ nanoneedles, compared to conventional nanoparticles. The ultrathin nanoneedles are successfully introduced to a PEM electrolyzer single cell with the enhanced cell performance.     

Surface Reconstruction of Ni–Fe Layered Double Hydroxide Inducing Chloride Ion Blocking Materials for Outstanding Overall Seawater Splitting

Generation of hydrogen fuel via electrochemical water splitting powered by sustainable energy, such as wind or solar energy, is an attractive path toward the future renewable energy landscape. However, current water electrolysis requires desalinated water resources, eventually leading to energy costs and water scarcity. The development of cost-effective electrocatalysts capable of splitting saline water feeds directly can be an evident solution. Herein, a surface reconstructed nickel-iron layered double hydroxide (NF-LDH) is reported as an exceptionally active and durable bifunctional electrocatalyst for saline water splitting without chloride corrosion. The surface reconstructed NF-LDH consists of Ni₃Fe alloy phase interconnected in a 2D network in which an ultrathin (≈2 nm) and low-crystalline NiFe (oxy)hydroxide phase are formed on the surface. The NiFe (oxy)hydroxide phase draws large anodic current densities, satisfying the level of practical application, while the Ni₃Fe alloy phase is simultaneously responsible for the high catalytic activity for cathodic reactions and superior corrosion resistance. The surface reconstructed NF-LDH electrode can be easily fabricated in a large electrode area (up to 25 cm²) and can successfully produce hydrogen fuels from saline water powered by the laboratory-made low-intensity photovoltaic cell.     

Bifunctional Covalent Organic Framework-Derived Electrocatalysts with Modulated p-Band Centers for Rechargeable Zn–Air Batteries

Fine control over the physicochemical structures of carbon electrocatalysts is important for improving the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Zn–air batteries. Covalent organic frameworks (COFs) are considered good candidate carbon materials because their structures can be precisely controlled. However, it remains a challenge to impart bifunctional electrocatalytic activities for both the ORR and OER to COFs. Herein, a pyridine-linked triazine covalent organic framework (PTCOF) with well-defined active sites and pores is readily prepared under mild conditions, and its electronic structure is modulated by incorporating Co nanoparticles (CoNP-PTCOF) to induce bifunctional electrocatalytic activities for the ORR and OER. The CoNP-PTCOF exhibits lower overpotentials for both ORR and OER with outstanding stability. Computational simulations find that the p-band center of CoNP-PTCOF down-shifted by charge transfer, compared to pristine PTCOF, facilitate the adsorption and desorption of oxygen intermediates on the pyridinic carbon active sites during the reactions. The Zn–air battery assembled with bifunctional CoNP-PTCOF exhibits a small voltage gap of 0.83 V and superior durability for 720 cycles as compared with a battery containing commercial Pt/C and RuO₂. This strategy for modulating COF electrocatalytic activities can be extended for designing diverse carbon electrocatalysts.     

Recent Advances in Atomic‐Level Engineering of Nanostructured Catalysts for Electrochemical CO2 Reduction

Electrochemical reduction of CO₂ into value‐added chemicals provides a promising approach to mitigate climate change caused by CO₂ from excess consumption of fossil fuels. As the CO₂ molecule is chemically inert and the reaction kinetics is sluggish, efficient electrocatalysts are thus highly required for promoting the conversion of CO₂. With great efforts devoted to improving the catalytic performance, the development of electrocatalysts for CO₂ reduction has gone from bulk metals with poor control to nanostructures with atomic precision. Nanostructured electrocatalysts with atomic precision are believed to be capable of combining the advantages of heterogeneous and homogenous catalysts. In this review, the recent advances in designing nanostructured electrocatalysts at the atomic level for boosting the catalytic performance toward CO₂ reduction and revealing the structure–property relationship are summarized. The challenges and opportunities in the near future are also proposed for paving the development of electrocatalytic CO₂ reduction.     

Sandwich‐Like Nanocomposite of CoNiOx/Reduced Graphene Oxide for Enhanced Electrocatalytic Water Oxidation

The development of cost‐effective and high‐performance electrocatalysts for oxygen evolution reaction (OER) is essential for sustainable energy storage and conversion processes. This study reports a novel and facile approach to the hierarchical‐structured sheet‐on‐sheet sandwich‐like nanocomposite of CoNiO _x /reduced graphene oxide as highly active electrocatalysts for water oxidation. Notably, the as‐prepared composite can operate smoothly both in 0.1 and 1.0 m KOH alkaline media, displaying extremely low overpotentials, fast kinetics, and strong durability over long‐term continuous electrolysis. Impressively, it is found that its catalytic activity can be further promoted by anodic conditioning owing to the in situ generation of electrocatalytic active species (i.e., metal hydroxide/(oxy)hydroxides) and the enriched oxygen deficiencies at the surface. The achieved ultrahigh performance is unmatched by most of the transition‐metal/nonmetal‐based catalysts reported so far, and even better than the state‐of‐the‐art noble‐metal catalysts, which can be attributed to its special well‐defined physicochemical textural features including hierarchical architecture, large surface area, porous thin nanosheets constructed from CoNiO _x nanoparticles (≈5 nm in size), and the incorporation of charge‐conducting graphene. This work provides a promising strategy to develop earth‐abundant advanced OER electrocatalysts to replace noble metals for a multitude of renewable energy technologies.