Engineering of the Heterointerface of Porous Carbon Nanofiber–Supported Nickel and Manganese Oxide Nanoparticle for Highly Efficient Bifunctional Oxygen Catalysis

Constructing heterointerfaces between metals and metal compounds is an attractive strategy for the fabrication of high performance electrocatalysts. However, realizing the high degree of fusion of two different metal components to form heterointerfaces remains a great challenge, since the different metal components tend to grow separately in most cases. Herein, by employing carboxyl‐modified carbon nanotubes to stabilize different metal ions, the engineering of abundant Ni|MnO heterointerfaces is achieved in porous carbon nanofibers (Ni|MnO/CNF) during the electrospinning–calcination process. Remarkably, the resulting Ni|MnO/CNF catalyst exhibits activities that are among the best reported for the catalysis of both the oxygen reduction and oxygen evolution reactions. Moreover, the catalyst also demonstrates high power density and long cycle life in Zn–air batteries. Its superior electrochemical properties are mainly ascribed to the synergy between the engineering of oxygen‐deficient Ni|MnO heterointerfaces with a strong Ni/Mn alloying interaction and the 1D porous CNF support. This facile anchoring strategy for the initiation of bimetallic heterointerfaces creates appealing opportunities for the potential use of heteronanomaterials in practical sustainable energy applications.     

Symmetric Electronic Structures of Active Sites to Boost Bifunctional Oxygen Electrocatalysis by MN4+4 Sites Directly from Initial Covalent Organic Polymers

Transition metal-nitrogen-carbon (M-N-C) catalysts with CoN₄ centers have attracted great attention as a potential alternative to precious metal catalysts for bifunctional oxygen electrocatalysis. However, the asymmetric charge environment of the active site of MN₄ obtained by conventional pyrolysis strategy makes the unbalanced adsorption of oxygen molecules, which restricts the activities of both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, a series of well-defined quasi-phthalocyanine conjugated 2D covalent organic polymer (COP_BTC-M) is developed with MN₄₊₄ active sites through a pyrolysis-free strategy. Compared to CoN₄ site, the additional subcentral N₄ atoms in MN₄₊₄ site in COP_BTC-Co catalyst balance the charge environment and form a symmetric charge distribution, which changes the antibonding orbital of the active metal and regulate the oxygen species adsorption, thus improving the activity of the bifunctional oxygen electrocatalysis. In Silico screening demonstrates that cobalt has the best ORR and OER activity for COP_BTC-M with MN₄₊₄ sites, which can be attributed to the fewer anti-bonding orbital below the Fermi level, which weakens the oxygen species adsorption. Both theoretical and experimental results verify that the COP_BTC-Co possesses unique CoN₄₊₄ active sites and the harmonious coordinating environment can lead to superior bifunctional oxygen catalytic activity with a high bifunctional oxygen catalytic activity (ΔE [Ej₁₀ – E_1/2] = 0.76 V), which is comparable with the benchmark Pt/C-IrO₂ pairs. Accordingly, the as-assembled Zn–air battery exhibits a maximum power density of 157.7 mW cm ⁻² with stable operation for >100 cycles under an electric density of 10 mA cm ⁻². This study provides a characteristic understanding of the intrinsic active species toward MN_x centers and could inspire new avenues for designation of advanced bifunctional electrocatalysts that catalyze ORR and OER processes simultaneously.     

Anchoring Single Copper Atoms to Microporous Carbon Spheres as High-Performance Electrocatalyst for Oxygen Reduction Reaction

Although the carbon-supported single-atom (SA) electrocatalysts (SAECs) have emerged as a new form of highly efficient oxygen reduction reaction (ORR) electrocatalysts, the preferable sites of carbon support for anchoring SAs are somewhat elusive. Here, a KOH activation approach is reported to create abundant defects/vacancies on the porous graphitic carbon nanosphere (CNS) with selective adsorption capability toward transition-metal (TM) ions and innovatively utilize the created defects/vacancies to controllably anchor TM–SAs on the activated CNS via TM N_x coordination bonds. The synthesized TM-based SAECs (TM-SAs@N-CNS, TM: Cu, Fe, Co, and Ni) possess superior ORR electrocatalytic activities. The Cu-SAs@N-CNS demonstrates excellent ORR and oxygen evolution reaction (OER) bifunctional electrocatalytic activities and is successfully applied as a highly efficient air cathode material for the Zn–air battery. Importantly, it is proposed and validated that the N-terminated vacancies on graphitic carbons are the preferable sites to anchor Cu-SAs via a Cu (N C₂)₃(N C) coordination configuration with an excellent promotional effect toward ORR. This synthetic approach exemplifies the expediency of suitable defects/vacancies creation for the fabrication of high-performance TM-based SAECs, which can be implemented for the synthesis of other carbon-supported SAECs.     

High-Density Atomic Fe–N4/C in Tubular,Biomass-Derived,Nitrogen-Rich Porous Carbon as Air-Electrodes for Flexible Zn–Air Batteries

Developing low-cost single-atom catalysts (SACs) with high-density active sites for oxygen reduction/evolution reactions (ORR/OER) are desirable to promote the performance and application of metal–air batteries. Herein, the Fe nanoparticles are precisely regulated to Fe single atoms supported on the waste biomass corn silk (CS) based porous carbon for ORR and OER. The distinct hierarchical porous structure and hollow tube morphology are critical for boosting ORR/OER performance through exposing more accessible active sites, providing facile electron conductivity, and facilitating the mass transfer of reactant. Moreover, the enhanced intrinsic activity is mainly ascribed to the high Fe single-atom (4.3 wt.%) loading content in the as-synthesized catalyst.Moreover, the ultra-high N doping (10 wt.%) can compensate the insufficient OER performance of conventional Fe N C catalysts. When as-prepared catalysts are assembled as air-electrodes in flexible Zn–air batteries, they perform a high peak power density of 101 mW cm⁻², a stable discharge–charge voltage gap of 0.73 V for >44 h, which shows a great potential for Zinc–air battery. This work provides an avenue to transform the renewable low-cost biomass materials into bifunctional electrocatalysts with high-density single-atom active sites and hierarchical porous structure.     

Sulfur Mismatch Substitution in Layered Double Hydroxides as Efficient Oxygen Electrocatalysts for Flexible Zinc–Air Batteries

Although layered double hydroxides (LDHs) are extensively investigated for oxygen electrocatalysis, their development is hampered by their limited active sites and sluggish reaction kinetics. Here, sulfur mismatch substitution of NiFe–LDH (S–LDH) is demonstrated, which are in-situ deposited on nitrogen-doped graphene (S–LDH/NG). This atomic-level sulfur incorporation leads to the construction of the tailored topological microstructure and the modulated electronic structure for the improved catalytic activity and durability of bifunctional electrocatalysts. The combined computational and experimental results clarify that the electron transfer between the sulfur anion and Fe³⁺ generates the high-valence Fe⁴⁺ species, while the mismatch substitution of the sulfur anion induces the metallic conductivity, an increased carrier density, and the reduced reaction barrier. Consequently, the as-fabricated Zn–air battery achieves a high power density of 165 mW cm^-2, a large energy density of 772 Wh kg_Zn^-1 at 5 mA cm^-2, and long cycle stability for 120 h, demonstrating its real-life operation.     

Dual-Phasic Carbon with Co Single Atoms and Nanoparticles as a Bifunctional Oxygen Electrocatalyst for Rechargeable Zn–Air Batteries

The great interest in rechargeable Zn–air batteries (ZABs) arouses extensive research on low-cost, high-active, and durable bifunctional electrocatalysts to boost the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). It remains a great challenge to simultaneously host high-active and independent ORR and OER sites in a single catalyst. Herein a dual-phasic carbon nanoarchitecture consisting of a single-atom phase for the ORR and nanosized phase for the OER is proposed. Specifically, single Co atoms supported on carbon nanotubes (single-atom phase) and nanosized Co encapsulated in zeolitic-imidazole-framework-derived carbon polyhedron (nanosized phase) are integrated together via carbon nanotube bridges. The obtained dual-phasic carbon catalyst shows a small overpotential difference of 0.74 V between OER potential at 10 mA cm⁻² and ORR half-wave potential. The ZAB based on the bifunctional catalyst demonstrates a large power density of 172 mW cm⁻². Furthermore, it shows a small charge-discharge potential gap of 0.51 V at 5 mA cm⁻² and outstanding discharge-charge cycling durability. This study provides a feasible design concept to achieve multifunctional catalysts and promotes the development of rechargeable ZABs.     

Engineering Crystallinity and Oxygen Vacancies of Co(II) Oxide Nanosheets for High Performance and Robust Rechargeable Zn–Air Batteries

Efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) processes highly rely on the rational design and synthesis of high-performance electrocatalysts. Herein, comprehensive characterizations and density functional theory (DFT) calculations are combined to verify the important roles of the crystallinity and oxygen vacancy levels of Co(II) oxide (CoO) on ORR and OER activities. A facile and controllable vacuum-calcination strategy is utilized to convert Co(OH)₂ into oxygen-defective amorphous-crystalline CoO (namely ODAC-CoO) nanosheets. With the carefully controlled crystallinity and oxygen vacancy levels, the optimal ODAC-CoO sample exhibits dramatically enhanced ORR and OER electrocatalytic activities compared with the pure crystalline CoO counterpart. The assembled liquid and quasi-solid-state Zn–air batteries with ODAC-CoO as cathode material achieve remarkable specific capacity, power density, and excellent cycling stability, outperforming the benchmark Pt/C + IrO₂ catalysts. This study theoretically proposes and experimentally demonstrates that the simultaneous introduction of amorphous structures and oxygen vacancies could be an effective avenue towards high-performance electrocatalytic ORR and OER.     

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.     

A Low-Cost,Durable Bifunctional Electrocatalyst Containing Atomic Co and Pt Species for Flow Alkali-Al/Acid Hybrid Fuel Cell and Zn–Air Battery

Transition metal single atoms anchored on nitrogen-doped carbon (M-N-C) matrix with M-N-C active sites have shown to be promising catalysts for both hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). Herein, a hybrid catalyst with low-level loading of atomic Pt and Co species encapsulated in nitrogen-doped graphene (Pt@CoN₄-G) is developed. The Pt@CoN₄-G shows low overpotential for HER in wide-pH electrolyte and manifests improved mass activity with almost eight times greater than that of Pt/C at an overpotential of 50 mV. The Pt@CoN₄-G also exhibits a top-level ORR activity (half-wave potential, E_1/2 = 0.893 V) and robust stability (>200 h) in alkaline medium. Using theoretical calculations and comprehensive characterizations , the strong metal–support interactions between Pt species and CoN₄-G support and synergistical cooperation of multiple active sites are clarified. A flow alkali-Al/acid hybrid fuel cell using Pt@CoN₄-G as cathode catalyst delivers a large power density of 222 mW cm⁻² with excellent stability to achieve simultaneously hydrogen evolution and electricity generation. In addition, Pt@CoN₄-G endows a flow Zn-air battery with high power density (316 mW cm⁻²), good stability under large current density (>100 h at 100 mA cm⁻²), and long cycle life (over 600 h at 5 mA cm⁻²).     

Electrospinning Synthesis of Self-Standing Cobalt/Nanocarbon Hybrid Membrane for Long-Life Rechargeable Zinc–Air Batteries

Integrating high-efficiency oxygen electrocatalyst directly into air electrodes is vital for zinc–air batteries to achieve higher electrochemical performance. Herein, a self-standing membrane composed of hierarchical cobalt/nanocarbon nanofibers is fabricated by the electrospinning technique. This hybrid membrane can be directly employed as the bifunctional air electrode in zinc–air batteries and can achieve a high peak power density of 304 mW cm⁻² with a long service life of 1500 h at 5 mA cm⁻². Its assembled solid-state zinc–air battery also delivers a promising power density of 176 mW cm⁻² with decent flexibility. The impressive rechargeable battery performance would be attributed to the self-standing membrane architecture integrated by oxygen electrocatalysts with abundant cobalt–nitrogen–carbon active species in the hierarchical electrode. This study may provide effective electrospinning solutions in integrating efficient electrocatalyst and electrode for energy storage and conversion technologies.     

MnO Enabling Highly Efficient and Stable Co-Nx/C for Oxygen Reduction Reaction in both Acidic and Alkaline Media

In situ growing transition metals on N-doped carbon by atomic doping produces a class of promising alternatives to replace Pt-based catalysts for redox reactions, yet still suffer from unsatisfactory activity and durability in acidic and basic media. Herein, a simple synthetic strategy to fabricate an MnO modifying Co-N_x/C catalyst with high activity and robust durability is presented. The interphase engineering well controls the Co and N species in the carbon matrix, affording the material with more pyridine N and graphite N; the interaction between Co-N_x and MnO phase is also well discussed. Accordingly, the obtained Co-N_x/C-MnO catalyst exhibits excellent electrocatalytic properties towards oxygen reduction reaction, achieving a half-wave potential of 0.87 and 0.66 V versus reversible hydrogen electrode in 0.1 m KOH and 0.1 m HClO₄ solutions, as well as excellent durability with only −16.9 and −12.2 mV shift after 1000 cycles, respectively. This study provides insights into the design of noble-metal-free electrocatalysts from the perspective of active sites and catalyst carriers.     

Dual Evolution in Defect and Morphology of Single-Atom Dispersed Carbon Based Oxygen Electrocatalyst

The structure design and atomic modulation of catalysts are two sides of the same coin, both of which are deemed critical factors to regulate the intrinsic electrocatalytic activity. Herein, cobalt single-atom anchored on nitrogen-doped graphene-sheet@tube (CoSAs-NGST) is derived from a novel Co, Zn-coordinated zeolitic imidazolate framework (CoZn-ZIF) in the presence of dicyandiamide. CoSAs-NGST exhibited a hybrid structure with a bamboo-like graphene tube and sheet. The atomic configuration of intrinsic defects is characterized by electron energy loss spectroscopy. The morphology differentiation from cake-shape structure to low-dimension hybrid not only enhances the dispersity of single atoms but also induces defect state evolution, which results in the formation of a CoN₄-rich graphene tube. Density functional theory (DFT) modeling revealed that the coupling effect on oxygen reduction reaction and oxygen evolution reaction (ORR/OER) pathways of Co-N₄-tube and Co-N₄-sheet is responsible for the enhanced activity of CoSAs-NGST. In addition to the superb ORR/OER bifunctional catalytic performance, CoSAs-NGST also demonstrates a notably small charge–discharge voltage drop of 0.93 V when applied in the rechargeable zinc–air battery outperforming Pt/C + RuO₂ catalyst. The present study provides an insight into the relationship between the structure design and atomic modulation of the carbon based catalysts.     

Modulating Electronic Structure of Atomically Dispersed Nickel Sites through Boron and Nitrogen Dual Coordination Boosts Oxygen Reduction

Atomically dispersed 3D transitional metal active sites with nitrogen coordination anchored on carbon support have emerged as a kind of promising electrocatalyst toward oxygen reduction reaction (ORR) in the field of fuel cells and metal–air cells. However, it is still a challenge to accurately modulate the coordination structure of single-atom metal sites, especially first-shell coordination, as well as identify the relationship between the geometric/electronic structure and ORR performance. Herein, a carbon-supported single-atom nickel catalyst is fabricated with boron and nitrogen dual coordination (denoted as Ni-B/N-C). The hard X-ray absorption spectrum result reveals that atomically dispersed Ni active sites are coordinated with one B atom and three N atoms in the first shell (denoted as Ni-B₁N₃). The Ni-B/N-C catalyst exhibits a half-wave potential (E_1/2) of 0.87 V versus RHE, along with a distinguished long-term durability in alkaline media, which is superior to commercial Pt/C. Density functional theory calculations indicate that the Ni-B₁N₃ active sites are more favorable for the adsorption of ORR intermediates relative to Ni-N₄, leading to the reduction of thermodynamic barrier and the acceleration of reaction kinetics, which accounts for the increased intrinsic activity.     

Assembling Amorphous Metal–Organic Frameworks onto Heteroatom-Doped Carbon Spheres for Remarkable Bifunctional Oxygen Electrocatalysis

Multifunctional electrocatalysts play an increasingly crucial role in various practical electrochemical energy conversion devices. Especially, on the air cathode of rechargeable zinc–air batteries (ZABs), oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), requiring efficient bifunctional electrocatalysts, are switched during discharging and charging process. Here, supported by the theoretical computations, a facile strategy for the in situ assembly of NiFe-MOFs nanosheets on heteroatoms-doped porous activated carbon spheres is developed. The newly designed electrocatalyst (NP-ACSs@NiFe-MOFs) shows excellent performance toward bifunctional oxygen electrocatalysis. Specifically, a remarkable low value of potential gap (ΔE = 0.61 V), which is the difference between the potential to reach an OER current density of 10 mA cm⁻² and ORR half-wave potential, is achieved in 0.1 m KOH. Notably, the aqueous ZAB based on NP-ACSs@NiFe-MOFs shows super cycle stability with small voltage gap of only 0.79 V when cycled for 450 h at 10 mA cm⁻². Also, the quasi-solid-state ZAB indicates excellent flexibility and cycling stability. This study presents a facile strategy for the rational integration of different catalytically active components, and can be extended to prepare other strongly competitive multifunctional electrocatalysts.     

One‐Pot Synthesis of Framework Porphyrin Materials and Their Applications in Bifunctional Oxygen Electrocatalysis

Organic framework materials constructed by covalently linking organic building blocks into framework structures are highly regarded as paragons to precisely control the material structure at the atomic level. Herein, a direct synthesis methodology is proposed as a guidance for the bulk synthesis of organic framework materials. Framework porphyrin (POF) materials are one‐pot synthesized to demonstrate the advances of the direct synthesis methodology. The as‐synthesized POF materials are intrinsically 2D and exhibit impressive versatility in composition, structure, morphology, and function, delivering a free‐standing POF film, hybrids of POF and nanocarbon, and cobalt‐coordinated POF. When applied as electrocatalysts for oxygen reduction reaction and oxygen evolution reaction, the cobalt‐coordinated POF exhibits excellent bifunctional electrocatalytic performances comparable with noble‐metal‐based electrocatalysts. The direct synthesis methodology and resultant POF materials demonstrate the ability of controlling materials at the atomic level for energy electrocatalysis.     

Regulating the Spin-State of Rare-Earth Ce Single Atom Catalyst for Boosted Oxygen Reduction in Neutral Medium

The development of neutral zinc–air batteries (ZABs) is long been impeded by the sluggish oxygen reduction reaction (ORR) derived from insufficient O₂ activation and OH* blocking effect. Herein, the synthesis of a series of rare-earth Ce single-atom catalysts (CeNCs) is reported with enhanced spin-state for boosting neutral ORR. Experimental analysis and theoretical calculations indicate that the unique local coordination/geometric structure reshapes the electronic configuration of Ce sites to achieve a transition from 4d¹⁰4f¹ to 4d⁸4f³. The high-spin Ce active sites accelerate the unpaired f electrons to occupy the anti-π orbitals of O₂ and generate suitable binding strength with reaction intermediates. In neutral conditions, CeNC-40 exhibits excellent ORR performance with half-wave potentials of 0.78 V and negligible decay after 10 000 cycles. Additionally, the self-breathing ZABs based on CeNC-40 demonstrates a peak power density of 81 mW cm⁻² and impressive long-cycle stability (>1 600 cycles) at 2 mA cm⁻². This work presents an effective strategy for developing high-spin catalysts to address the challenges of neutral ZABs.     

Confinement Synthesis Based on Layered Double Hydroxides: A New Strategy to Construct Single-Atom-Containing Integrated Electrodes

Highly efficient and low-cost electrodes have a key role in the development of advanced energy devices such as fuel cells and metal–air batteries. However, electrode performance is typically limited by low utilization of active sites, which causes a considerable drop in energy density. To overcome this issue, a single-atom-containing integrated electrode is developed through a confinement synthesis strategy by using organic molecule-intercalated layered double hydroxides (LDHs) as precursors. The as-prepared integrated electrode has a well-defined nanosheet array structure with a homogeneous anchored single atomic Co catalyst and many exposed hierarchical pores. Moreover, the coordination environment of single atoms (Co N or Co S) is precisely controlled by regulating the type of interlayer molecules in the LDHs. Consequently, the optimized electrode exhibits high bifunctional activity toward both the oxygen reduction and oxygen evolution reactions. This electrode is directly assembled into an all-solid-state zinc–air battery that showed outstanding flexibility and long-term charge/discharge stability. Because of the versatility of LDH materials, it is expected that the proposed strategy can be extended to the construction of other integrated electrodes for high-performance energy storage and conversion devices.     

Advanced Oxygen Electrocatalysis in Energy Conversion and Storage

Oxygen electrocatalysis is of great significance in electrochemical energy conversion and storage. Many strategies have been adopted for developing advanced oxygen electrocatalysts to promote these technologies. In this invited contribution, recent progress in understanding the oxygen electrochemistry from theoretical and experimental aspects is summarized. The major categories of oxygen electrocatalysts, namely, noble-metal-based compounds, transition-metal-based composites, and nanocarbons, are successively discussed for oxygen reduction and evolution. Design strategies of various oxygen electrocatalysts and their relationship on the structure–activity–performance are comprehensively addressed with the perspectives. Finally, the challenge and outlook for advanced oxygen electrocatalysts are discussed toward energy conversion and storage technologies.     

Constructing Asymmetrical Coordination Microenvironment with Phosphorus-Incorporated Nitrogen-Doped Carbon to Boost Bifunctional Oxygen Electrocatalytic Activity

Carbon-based metal-free electrocatalysts have been recognized as inexpensive alternatives to afford excellent activity in oxygen reduction/evolution reactions (ORR/OER). Nevertheless, precisely identifying the local active sites and tailoring the corresponding electronic properties to enhance the reaction kinetics remain challenging. Herein, a facile strategy to create a metal-free electrocatalyst comprised of a mesoporous nitrogen-doped carbon matrix with phosphorus incorporation (NPC) is described. The as-prepared NPC-950 electrocatalyst demonstrates superior ORR activity under alkaline and acidic conditions with half-wave potentials of 0.88 and 0.72 V, respectively, comparable to commercial Pt/C (0.85 and 0.76 V) and overwhelmingly superior to other N-doped carbon catalyst materials. In addition, a remarkable promotion of OER activity under alkaline conditions is observed. Notably, a zinc–air battery equipped with this NCP-950 electrocatalyst exhibits exceptional performance in peak power density, specific capacity, and long-term operation durability. Theoretical calculations uncover that the incorporation of phosphorus in NC material results in effective charge density redistribution, thus modulating the electronic properties of active sites to achieve optimum adsorption and desorption of ORR intermediates. The work provides a deep understanding of active sites in heteroatom-doped carbon materials and highlights the importance of the electronic properties modulation in oxygen bifunctional electrocatalytic activity.     

Hollow Multivoid Nanocuboids Derived from Ternary Ni–Co–Fe Prussian Blue Analog for Dual‐Electrocatalysis of Oxygen and Hydrogen Evolution Reactions

Hydrogen generation from electrochemical water‐splitting is an attractive technology for clean and efficient energy conversion and storage, but it requires efficient and robust non‐noble electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER). Nonprecious transition metal–organic frameworks (MOFs) are one of the most promising precursors for developing advanced functional catalysts with high porosity and structural rigidity. Herein, a new transition metal‐based hollow multivoid nanocuboidal catalyst synthesized from a ternary Ni–Co–Fe (NCF)‐MOF precursor is rationally designed to produce dual‐functionality toward OER and HER. Differing ion exchanging rates of the ternary transition metals within the prussian blue analog MOF precursor are exploited to produce interconnected internal voids, heteroatom doping, and a favorably tuned electronic structure. This design strategy significantly increases active surface area and pathways for mass transport, resulting in excellent electroactivities toward OER and HER, which are competitive with recently reported single‐function nonprecious catalysts. Moreover, outstanding electrochemical durability is realized due to the unique rigid and interconnected porous structure which considerably retains initial rapid charge transfer and mass transport of active species. The MOF‐based material design strategy demonstrated here exemplifies a novel and versatile approach to developing non‐noble electrocatalysts with high activity and durability for advanced electrochemical water‐splitting systems.