Super‐Exchange Interaction Induced Overall Optimization in Ferromagnetic Perovskite Oxides Enables Ultrafast Water Oxidation

Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal–air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super‐exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition‐dependent OER activity in SrCo_1x Ru_x O_3?δ (denoted as SCRx) (x = 0.0–1.0) perovskite is displayed with special attention on the role of super‐exchange interaction between high spin (HS) Co³⁺ and Ru⁵⁺ ions. Induced by the unique Co³⁺–O–Ru⁵⁺ super‐exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co³⁺/Co⁴⁺, Ru⁵⁺, and O₂^2?/O^?, high electrical conductivity, and metal–oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm^?2, which exceeds the benchmark RuO₂ and most well‐known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.     

Reducing the Barrier Energy of Self‐Reconstruction for Anchored Cobalt Nanoparticles as Highly Active Oxygen Evolution Electrocatalyst

It is crucial for leaping forward renewable energy technology to develop highly active oxygen evolution reaction (OER) catalysts with fast OER kinetics, and the novel design of high‐performance catalysts may come down to unveiling the origin of high catalytic behavior. Herein, a new class of heterogeneous OER electrocatalyst (metallic Co nanoparticles anchored on yttrium ruthenate pyrochlore oxide) is provided for securing fast OER kinetics. In situ X‐ray absorption spectroscopy (in situ XAS) reveals that fast OER kinetics can be achieved by the harmonious catalytic synergy of a pyrochlore oxide support to Co nanoparticles. By the facile oxidation of yttrium (A‐site) and ruthenium (B‐site) cations, the pyrochlore oxide support helps to expel the electrons generated from the catalytic behavior of Co to the inner layers of the support, facilitating the electrostatic adsorption of OH^? ions and reducing the barrier energy for the formation of CoOOH intermediates. This work affords the rational design of transition metal nanoparticles anchored on pyrochlore oxide heterogeneous catalysts and the fundamental insight of catalytic origin associated with self‐reconstruction of OER electrocatalysts.     

Amorphous Cobalt Phyllosilicate with Layered Crystalline Motifs as Water Oxidation Catalyst

The development of a high‐performance oxygen evolution reaction (OER) catalyst is pivotal for the practical realization of a water‐splitting system. Although an extensive search for OER catalysts has been performed in the past decades, cost‐effective catalysts remain elusive. Herein, an amorphous cobalt phyllosilicate (ACP) with layered crystalline motif prepared by a room‐temperature precipitation is introduced as a new OER catalyst; this material exhibits a remarkably low overpotential (η ≈ 367 mV for a current density of 10 mA cm^?2). A structural investigation using X‐ray absorption spectroscopy reveals that the amorphous structure contains layered motifs similar to the structure of CoOOH, which is demonstrated to be responsible for the OER catalysis based on density functional theory calculations. However, the calculations also reveal that the local environment of the active site in the layered crystalline motif in the ACP is significantly modulated by the silicate, leading to a substantial reduction of η of the OER compared with that of CoOOH. This work proposes amorphous phyllosilicates as a new group of efficient OER catalysts and suggests that tuning of the catalytic activity by introducing redox‐inert groups may be a new unexplored avenue for the design of novel high‐performance catalysts.     

Self‐Assembled Ruddlesden–Popper/Perovskite Hybrid with Lattice‐Oxygen Activation as a Superior Oxygen Evolution Electrocatalyst

The oxygen evolution reaction (OER) is pivotal in multiple gas‐involved energy conversion technologies, such as water splitting, rechargeable metal–air batteries, and CO₂/N₂ electrolysis. Emerging anion‐redox chemistry provides exciting opportunities for boosting catalytic activity, and thus mastering lattice‐oxygen activation of metal oxides and identifying the origins are crucial for the development of advanced catalysts. Here, a strategy to activate surface lattice‐oxygen sites for OER catalysis via constructing a Ruddlesden–Popper/perovskite hybrid, which is prepared by a facile one‐pot self‐assembly method, is developed. As a proof‐of‐concept, the unique hybrid catalyst (RP/P‐LSCF) consists of a dominated Ruddlesden–Popper phase LaSr₃Co_1.5Fe_1.5O_10‐δ (RP‐LSCF) and second perovskite phase La_0.25Sr_0.75Co_0.5Fe_0.5O_3‐δ (P‐LSCF), displaying exceptional OER activity. The RP/P‐LSCF achieves 10 mA cm^?2 at a low overpotential of only 324 mV in 0.1 m KOH, surpassing the benchmark RuO₂ and various state‐of‐the‐art metal oxides ever reported for OER, while showing significantly higher activity and stability than single RP‐LSCF oxide. The high catalytic performance for RP/P‐LSCF is attributed to the strong metal–oxygen covalency and high oxygen‐ion diffusion rate resulting from the phase mixture, which likely triggers the surface lattice‐oxygen activation to participate in OER. The success of Ruddlesden–Popper/perovskite hybrid construction creates a new direction to design advanced catalysts for various energy applications.     

Cytomembrane‐Structure‐Inspired Active Ni–N–O Interface for Enhanced Oxygen Evolution Reaction

Surface/interface design is one of the most significant and promising motivations to develop high‐performance catalysts for electrolytic water splitting. Here, the nature of cytomembrane having the most effective and functional surface structure is mimicked to fabricate a new configuration of Ni–N–O porous interface nanoparticles (NiNO INPs) with strongly interacting nanointerface between the Ni₃N and NiO domains, for enhancing the electrocatalytic oxygen evolution reaction (OER) performance. The combination of transmission electron microscopy and electrochemical investigations, tracking the correlation between microstructure evolution and catalytic activity, demonstrate the strongly coupled nanointerface for an approximately sixfold improvement of electrolytic efficiency. Density functional theory simulates the electrocatalytic process with a maximum of 85% reduction of the energy barrier. Further investigations find that the real active site for the OER in the NiNO INPs is the strongly coupled Ni–N–O nanointerface, not the derived amorphous hydroxide, during the OER process. The determination of the correlation of constructed nanointerface with catalytic properties suggests a significant strategy toward the rational design of catalysts for efficient water electrocatalysis.     

Amorphous Intermediate Derivative from ZIF‐67 and Its Outstanding Electrocatalytic Activity

Increasing active sites is an effective method to enhance the catalytic activity of catalysts. Amorphous materials have attracted considerable attention in catalysis because of their abundant catalytic active sites. Herein, a series of derivatives is prepared via the low‐temperature heat treatment of ZIF‐67 hollow sphere at different temperatures. An intermediate product with an amorphous structure is formed during transformation from ZIF‐67 to Co₃O₄ nanocrystallines when ZIF‐67 hollow sphere is heat treated at 260 °C for 3 h. The chemical composition of the amorphous derivative is similar to that of ZIF‐67, and the carbon and nitrogen contents of the amorphous derivative are obviously higher than those of crystalline samples obtained at 270 °C or higher. As electrocatalysts for the oxygen evolution reaction (OER) and nonenzymatic glucose sensing, the amorphous derivative exhibits significantly better catalytic activity than crystalline Co₃O₄ samples. The amorphous sample as an OER catalyst has a low overpotential of 352 mV at 10 mA cm^?2. The amorphous sample as an enzyme‐free glucose sensing catalyst can provide a low detection limit of 3.9 × 10^?6 m and a high sensitivity of 1074.22 µA mM^?1 cm^?2.     

Tracking Structural Self‐Reconstruction and Identifying True Active Sites toward Cobalt Oxychloride Precatalyst of Oxygen Evolution Reaction

Unravelling the intrinsic mechanism of electrocatalytic oxygen evolution reaction (OER) by use of heterogeneous catalysts is highly desirable to develop related energy conversion technologies. Albeit dynamic self‐reconstruction of the catalysts during OER is extensively observed, it is still highly challenging to operando probe the reconstruction and precisely identify the true catalytically active components. Here, a new class of OER precatalyst, cobalt oxychloride (Co₂(OH)₃Cl) with unique features that allow a gradual phase reconstruction during OER due to the etching of lattice anion is demonstrated. The reconstruction continuously boosts OER activities. The reconstruction‐derived component delivers remarkable performance in both alkaline and neutral electrolytes. Operando synchrotron radiation‐based X‐ray spectroscopic characterization together with density functional theory calculations discloses that the etching of lattice Cl^? serves as the key to trigger the reconstruction and the boosted catalytic performance roots in the atomic‐level coordinatively unsaturated sites (CUS). This work establishes fundamental understanding on the OER mechanism associated with self‐reconstruction of heterogeneous catalysts.     

A Self‐Assembled Hetero‐Structured Inverse‐Spinel and Anti‐Perovskite Nanocomposite for Ultrafast Water Oxidation

Spinel and perovskite with distinctive crystal structures are two of the most popular material families in electrocatalysis, which, however, usually show poor conductivity, causing a negative effect on the charge transfer process during electrochemical reactions. Herein, a highly conductive inverse spinel (Fe₃O₄) and anti‐perovskite (Ni₃FeN) hetero‐structured nanocomposite is reported as a superior oxygen evolution electrocatalyst, which can be facilely prepared based on a one‐pot synthesis strategy. Thanks to the strong hybridization between Ni/Fe 3d and N 2p orbitals, the Ni₃FeN is easily transformed into NiFe (oxy)hydroxide as the real active species during the oxygen evolution reaction (OER) process, while the Fe₃O₄ component with low O‐p band center relative to Fermi level is structurally stable. As a result, both high surface reactivity and bulk electronic transport ability are reached. By directly growing Fe₃O₄/Ni₃FeN heterostructure on freestanding carbon fiber paper and testing based on the three‐electrode configuration, it requires only 160 mV overpotential to deliver a current density of 30 mA cm^?2 for OER. Also, negligible performance decay is observed within a prolonged test period of 100 h. This work sheds light on the rational design of novel heterostructure materials for electrocatalysis.     

Hydration-Effect-Promoting Ni–Fe Oxyhydroxide Catalysts for Neutral Water Oxidation

Oxygen evolution reaction (OER) catalysts that function efficiently in pH-neutral electrolyte are of interest for biohybrid fuel and chemical production. The low concentration of reactant in neutral electrolyte mandates that OER catalysts provide both the water adsorption and dissociation steps. Here it is shown, using density functional theory simulations, that the addition of hydrated metal cations into a Ni–Fe framework contributes water adsorption functionality proximate to the active sites. Hydration-effect-promoting (HEP) metal cations such as Mg²⁺ and hydration-effect-limiting Ba²⁺ into Ni–Fe frameworks using a room-temperature sol–gel process are incorporated. The Ni–Fe–Mg catalysts exhibit an overpotential of 310 mV at 10 mA cm⁻² in pH-neutral electrolytes and thus outperform iridium oxide (IrO₂) electrocatalyst by a margin of 40 mV. The catalysts are stable over 900 h of continuous operation. Experimental studies and computational simulations reveal that HEP catalysts favor the molecular adsorption of water and its dissociation in pH-neutral electrolyte, indicating a strategy to enhance OER catalytic activity.     

One‐Step In Situ Growth of Iron–Nickel Sulfide Nanosheets on FeNi Alloy Foils: High‐Performance and Self‐Supported Electrodes for Water Oxidation

Efficient and durable oxygen evolution reaction (OER) catalysts are highly required for the cost‐effective generation of clean energy from water splitting. For the first time, an integrated OER electrode based on one‐step direct growth of metallic iron–nickel sulfide nanosheets on FeNi alloy foils (denoted as Fe? Ni₃S₂/FeNi) is reported, and the origin of the enhanced OER activity is uncovered in combination with theoretical and experimental studies. The obtained Fe? Ni₃S₂/FeNi electrode exhibits highly catalytic activity and long‐term stability toward OER in strong alkaline solution, with a low overpotential of 282 mV at 10 mA cm^?2 and a small Tafel slope of 54 mV dec^?1. The excellent activity and satisfactory stability suggest that the as‐made electrode provides an attractive alternative to noble metal‐based catalysts. Combined with density functional theory calculations, exceptional OER performance of Fe? Ni₃S₂/FeNi results from a combination of efficient electron transfer properties, more active sites, the suitable O₂ evolution kinetics and energetics benefited from Fe doping. This work not only simply constructs an excellent electrode for water oxidation, but also provides a deep understanding of the underlying nature of the enhanced OER performance, which may serve as a guide to develop highly effective and integrated OER electrodes for water splitting.     

Zirconium‐Regulation‐Induced Bifunctionality in 3D Cobalt–Iron Oxide Nanosheets for Overall Water Splitting

The design of high‐efficiency non‐noble bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is paramount for water splitting technologies and associated renewable energy systems. Spinel‐structured oxides with rich redox properties can serve as alternative low‐cost OER electrocatalysts but with poor HER performance. Here, zirconium regulation in 3D CoFe₂O₄ (CoFeZr oxides) nanosheets on nickel foam, as a novel strategy inducing bifunctionality toward OER and HER for overall water splitting, is reported. It is found that the incorporation of Zr into CoFe₂O₄ can tune the nanosheet morphology and electronic structure around the Co and Fe sites for optimizing adsorption energies, thus effectively enhancing the intrinsic activity of active sites. The as‐synthesized 3D CoFeZr oxide nanosheet exhibits high OER activity with small overpotential, low Tafel slope, and good stability. Moreover, it shows unprecedented HER activity with a small overpotential of 104 mV at 10 mA cm^?2 in alkaline media, which is better than ever reported counterparts. When employing the CoFeZr oxides nanosheets as both anode and cathode catalysts for overall water splitting, a current density of 10 mA cm^?2 is achieved at the cell voltage of 1.63 V in 1.0 m KOH.     

NiMoFe and NiMoFeP as Complementary Electrocatalysts for Efficient Overall Water Splitting and Their Application in PV‐Electrolysis with STH 12.3%

Complementary water splitting electrocatalysts used simultaneously in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can simplify water splitting systems. Herein, earth‐abundant NiMoFe (NMF) and phosphorized NiMoFeP (NMFP) are synthesized as complementary overall water splitting (OWS) catalysts. First, NMF is tested as both the HER and OER promoter, which exhibits low overpotentials of 68 (HER) and 337 mV (OER). A quaternary NMFP is then prepared by simple phosphorization of NMF, which shows a much lower OER overpotential of 286 mV. The enhanced OER activity is attributed to the unique surface/core structure of NMFP. The surface phosphate acts as a proton transport mediator and expedites the rate‐determining step. With the application of OER potential, the NMFP surface is composed of Ni(OH)₂ and FeOOH, active sites for OER, but the inner core consists of Ni, Mo, and Fe metals, serving as a conductive electron pathway. OWS with NMF‐NMFP requires an applied voltage of 1.452 V to generate 10 mA cm^?2, which is one of the lowest values among OWS results with transition‐metal‐based electrocatalysts. Furthermore, the catalysts are combined with tandem perovskite solar cells for photovoltaic (PV)‐electrolysis, producing a high solar‐to‐hydrogen (STH) conversion efficiency of 12.3%.     

Iridium‐Based Multimetallic Porous Hollow Nanocrystals for Efficient Overall‐Water‐Splitting Catalysis

The development of active and durable bifunctional electrocatalysts for overall water splitting is mandatory for renewable energy conversion. This study reports a general method for controllable synthesis of a class of IrM (M = Co, Ni, CoNi) multimetallic porous hollow nanocrystals (PHNCs), through etching Ir‐based, multimetallic, solid nanocrystals using Fe³⁺ ions, as catalysts for boosting overall water splitting. The Ir‐based multimetallic PHNCs show transition‐metal‐dependent bifunctional electrocatalytic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic electrolyte, with IrCo and IrCoNi PHNCs being the best for HER and OER, respectively. First‐principles calculations reveal a ligand effect, induced by alloying Ir with 3d transition metals, can weaken the adsorption energy of oxygen intermediates, which is the key to realizing much‐enhanced OER activity. The IrCoNi PHNCs are highly efficient in overall‐water‐splitting catalysis by showing a low cell voltage of only 1.56 V at a current density of 2 mA cm^?2, and only 8 mV of polarization‐curve shift after a 1000‐cycle durability test in 0.5 m H₂SO₄ solution. This work highlights a potentially powerful strategy toward the general synthesis of novel, multimetallic, PHNCs as highly active and durable bifunctional electrocatalysts for high‐performance electrochemical overall‐water‐splitting devices.     

Constructing Pure Phase Tungsten‐Based Bimetallic Carbide Nanosheet as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting

Carbides are commonly regarded as efficient hydrogen evolution reaction (HER) catalysts, but their poor oxygen evolution reaction (OER) catalytic activities seriously limit their practical application in overall water splitting. Here, vertically aligned porous cobalt tungsten carbide nanosheet embedded in N‐doped carbon matrix (Co₆W₆C@NC) is successfully constructed on flexible carbon cloth (CC) as an efficient bifunctional electrocatalyst for overall water splitting via a facile metal–organic framework (MOF) derived method. The synergistic effect of Co and W atoms effectively tailors the electron state of carbide, optimizing the hydrogen‐binding energy. Thus Co₆W₆C@NC shows an enhanced HER performance with an overpotential of 59 mV at a current density of ?10 mA cm^?2. Besides, Co₆W₆C@NC easily in situ transforms into tungsten actived cobalt oxide/hydroxide during the OER process, serving as OER active species, which provides an excellent OER activity with an overpotential of 286 mV at a current density of ?10 mA cm^?2. The water splitting device, by applying Co₆W₆C@NC as both the cathode and anode, requires a low cell voltage of 1.585 V at 10 mA cm^?2 with the great stability in alkaline solution. This work provides a feasible strategy to fabricate bimetallic carbides and explores their possibility as bifunctional catalysts toward overall water splitting.     

ZIF‐8/ZIF‐67‐Derived Co‐Nx‐Embedded 1D Porous Carbon Nanofibers with Graphitic Carbon‐Encased Co Nanoparticles as an Efficient Bifunctional Electrocatalyst

Herein, an approach is reported for fabrication of Co‐N_x‐embedded 1D porous carbon nanofibers (CNFs) with graphitic carbon‐encased Co nanoparticles originated from metal–organic frameworks (MOFs), which is further explored as a bifunctional electrocatalyst for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Electrochemical results reveal that the electrocatalyst prepared by pyrolysis at 1000 °C (CoNC‐CNF‐1000) exhibits excellent catalytic activity toward ORR that favors the four‐electron ORR process and outstanding long‐term stability with 86% current retention after 40 000 s. Meanwhile, it also shows superior electrocatalytic activity toward OER, reaching a lower potential of 1.68 V at 10 mA cm^?2 and a potential gap of 0.88 V between the OER potential (at 10 mA cm^?2) and the ORR half‐wave potential. The ORR and OER performance of CoNC‐CNF‐1000 have outperformed commercial Pt/C and most nonprecious‐metal catalysts reported to date. The remarkable ORR and OER catalytic performance can be mainly attributable to the unique 1D structure, such as higher graphitization degree beneficial for electronic mobility, hierarchical porosity facilitating the mass transport, and highly dispersed CoN_xC active sites functionalized carbon framework. This strategy will shed light on the development of other MOF‐based carbon nanofibers for energy storage and electrochemical devices.     

Pseudocapacitive Ni‐Co‐Fe Hydroxides/N‐Doped Carbon Nanoplates‐Based Electrocatalyst for Efficient Oxygen Evolution

The oxygen evolution reaction (OER) catalytic activity of a transition metal oxides/hydroxides based electrocatalyst is related to its pseudocapacitance at potentials lower than the OER standard potential. Thus, a well‐defined pseudocapacitance could be a great supplement to boost OER. Herein, a highly pseudocapacitive Ni‐Fe‐Co hydroxides/N‐doped carbon nanoplates (NiCoFe‐NC)‐based electrocatalyst is synthesized using a facile one‐pot solvothermal approach. The NiCoFe‐NC has a great pseudocapacitive performance with 1849 F g^?1 specific capacitance and 31.5 Wh kg^?1 energy density. This material also exhibits an excellent OER catalytic activity comparable to the benchmark RuO₂ catalysts (an initiating overpotential of 160 mV and delivering 10 mA cm^?2 current density at 250 mV, with a Tafel slope of 31 mV dec^?1). The catalytic performance of the optimized NiCoFe‐NC catalyst could keep 24 h. X‐ray photoelectron spectroscopy, electrochemically active surface area, and other physicochemical and electrochemical analyses reveal that its great OER catalytic activity is ascribed to the Ni‐Co hydroxides with modular 2‐Dimensional layered structure, the synergistic interactions among the Fe(III) species and Ni, Co metal centers, and the improved hydrophily endowed by the incorporation of N‐doped carbon hydrogel. This work might provide a useful and general strategy to design and synthesize high‐performance metal (hydr)oxides OER electrocatalysts.     

Zinc Substitution‐Induced Subtle Lattice Distortion Mediates the Active Center of Cobalt Diselenide Electrocatalysts for Enhanced Oxygen Evolution

Doping engineering has been an important approach to boost oxygen evolution reaction (OER) activity, while investigation on the dopant‐induced modification of active sites and reaction kinetics remains incomplete. Herein, taking the cubic CoSe₂ as an example, a universal strategy to synergistically achieve active sites and dynamic regulation is developed by incorporating low‐valence Zn. It is revealed that regulation by Zn can facilitate reconstruction of the surface to form active Co oxyhydroxides under OER conditions. By combining theoretical calculations and characterization by various techniques, it is shown that the incorporation of Zn into CoSe₂ can cause subtle lattice distortion and strong electronic interactions, thereby contributing to increased active site exposure and improved OER kinetics. Density functional theory simulations demonstrate that Zn incorporation synergistically optimizes the kinetic energy barrier by promoting co‐adsorption of OER intermediates on a Co site and its adjacent Zn site. As a result, the modified CoSe₂ NAs electrode shows optimized catalytic activity and excellent stability with the low overpotential of only 286 mV required to drive a current density of 10 mA cm^?2 in an alkaline electrolyte.     

Enhanced Electrocatalytic Performance through Body Enrichment of Co‐Based Bimetallic Nanoparticles In Situ Embedded Porous N‐Doped Carbon Spheres

Extending available body space loading active species and controllably tailoring the d‐band center to Fermi level of catalysts are of paramount importance but extremely challenging for the enhancement of electrocatalytic performance. Herein, a melamine‐bridged self‐construction strategy is proposed to in situ embed Co‐based bimetallic nanoparticles in the body of N‐doped porous carbon spheres (CoM‐e‐PNC), and achieve the controllable tailoring of the d‐band center position by alloying of Co and another transition metal M (M = Ni, Fe, Mn, and Cu). The enrichment and exposure of the active sites in the body interior of porous carbon spheres, and the best balance between the adsorption of OH species and the desorption of O₂ induced by optimizing the d‐band center position, collectively enhance the oxygen evolution reaction (OER) performance. Meanwhile, the relationship of d‐band center position and OER activity is found to exhibit the volcano curve rule, where the CoNi‐e‐PNC catalyst shows optimal OER performance with an overpotential of 0.24 V at 10 mA cm^?2 in alkaline media, outperforming those of the ever‐reported CoNi‐based catalysts. Besides, CoNi‐e‐PNC catalyst also demonstrates high OER stability with slight current decrease after 100 h.     

Sugar Blowing‐Induced Porous Cobalt Phosphide/Nitrogen‐Doped Carbon Nanostructures with Enhanced Electrochemical Oxidation Performance toward Water and Other Small Molecules

Rational design of high active and robust nonprecious metal catalysts with excellent catalytic efficiency in oxygen evolution reaction (OER) is extremely vital for making the water splitting process more energy efficient and economical. Among these noble metal‐free catalysts, transition‐metal‐based nanomaterials are considered as one of the most promising OER catalysts due to their relatively low‐cost intrinsic activities, high abundance, and diversity in terms of structure and morphology. Herein, a facile sugar‐blowing technique and low‐temperature phosphorization are reported to generate 3D self‐supported metal involved carbon nanostructures, which are termed as Co₂P@Co/nitrogen‐doped carbon (Co₂P@Co/N‐C). By capitalizing on the 3D porous nanostructures with high surface area, homogeneously dispersed active sites, the intimate interaction between active sites, and 3D N‐doped carbon, the resultant Co₂P@Co/N‐C exhibits satisfying OER performance superior to CoO@Co/N‐C, delivering 10 mA cm^?2 at overpotential of 0.32 V. It is worth noting that in contrast to the substantial current density loss of RuO₂, Co₂P@Co/N‐C shows much enhanced catalytic activity during the stability test and a 1.8‐fold increase in current density is observed after stability test. Furthermore, the obtained Co₂P@Co/N‐C can also be served as an excellent nonprecious metal catalyst for methanol and glucose electrooxidation in alkaline media, further extending their potential applications.     

Single Fe Atom on Hierarchically Porous S,N‐Codoped Nanocarbon Derived from Porphyra Enable Boosted Oxygen Catalysis for Rechargeable Zn‐Air Batteries

Iron–nitrogen–carbon materials (Fe–N–C) are known for their excellent oxygen reduction reaction (ORR) performance. Unfortunately, they generally show a laggard oxygen evolution reaction (OER) activity, which results in a lethargic charging performance in rechargeable Zn–air batteries. Here porous S‐doped Fe–N–C nanosheets are innovatively synthesized utilizing a scalable FeCl₃‐encapsulated‐porphyra precursor pyrolysis strategy. The obtained electrocatalyst exhibits ultrahigh ORR activity (E_1/2 = 0.84 V vs reversible hydrogen electrode) and impressive OER performance (E_{j = 10} = 1.64 V). The potential gap (ΔE = E_{j = 10} ? E_1/2) is 0.80 V, outperforming that of most highly active bifunctional electrocatalysts reported to date. Furthermore, the key role of S involved in the atomically dispersed Fe–Nx species on the enhanced ORR and OER activities is expounded for the first time by ultrasound‐assisted extraction of the exclusive S source (taurine) from porphyra. Moreover, the assembled rechargeable Zn–air battery comprising this bifunctional electrocatalyst exhibits higher power density (225.1 mW cm^?2) and lower charging–discharging overpotential (1.00 V, 100 mA cm^?2 compared to Pt/C + RuO₂ catalyst). The design strategy can expand the utilization of earth‐abundant biomaterial‐derived catalysts, and the mechanism investigations of S doping on the structure–activity relationship can inspire the progress of other functional electrocatalysts.