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.     

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.     

Porous Carbon Membrane‐Supported Atomically Dispersed Pyrrole‐Type Fe?N4 as Active Sites for Electrochemical Hydrazine Oxidation Reaction

The rational design of catalytically active sites in porous materials is essential in electrocatalysis. Herein, atomically dispersed Fe‐N_x sites supported by hierarchically porous carbon membranes are designed to electrocatalyze the hydrazine oxidation reaction (HzOR), one of the key techniques in electrochemical nitrogen transformation. The high intrinsic catalytic activity of the Fe‐N_x single‐atom catalyst together with the uniquely mixed micro‐/macroporous membrane support positions such an electrode among the best‐known heteroatom‐based carbon anodes for hydrazine fuel cells. Combined with advanced characterization techniques, electrochemical probe experiments, and density functional theory calculation, the pyrrole‐type Fe? N₄ structure is identified as the real catalytic site in HzOR.     

Atomic Fe Dispersed on N‐Doped Carbon Hollow Nanospheres for High‐Efficiency Electrocatalytic Oxygen Reduction

Exploration of high‐efficiency, economical, and ultrastable electrocatalysts for the oxygen reduction reaction (ORR) to substitute precious Pt is of great significance in electrochemical energy conversion devices. Single‐atom catalysts (SACs) have sparked tremendous interest for their maximum atom‐utilization efficiency and fascinating properties. Therefore, the development of effective synthetic methodology toward SACs becomes highly imperative yet still remains greatly challenging. Herein, a reliable SiO₂‐templated strategy is elaborately designed to synthesize atomically dispersed Fe atoms anchored on N‐doped carbon nanospheres (denoted as Fe–N–C HNSs) using the cheap and sustainable biomaterial of histidine (His) as the N and C precursor. By virtue of the numerous atomically dispersed Fe–N₄ moieties and unique spherical hollow architecture, the as‐fabricated Fe–N–C HNSs exhibit excellent ORR performance in alkaline medium with outstanding activity, high long‐term stability, and superior tolerance to methanol crossover, exceeding the commercial Pt/C catalyst and most previously reported non‐precious‐metal catalysts. This present synthetic strategy will provide new inspiration to the fabrication of various high‐efficiency single‐atom catalysts for diverse applications.     

O‐, N‐Atoms‐Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts

Manganese (Mn) is generally regarded as not being sufficiently active for the oxygen reduction reaction (ORR) compared to other transition metals such as Fe and Co. However, in biology, manganese‐containing enzymes can catalyze oxygen‐evolving reactions efficiently with a relative low onset potential. Here, atomically dispersed O and N atoms coordinated Mn active sites are incorporated within graphene frameworks to emulate both the structure and function of Mn cofactors in heme–copper oxidases superfamily. Unlike previous single‐metal catalysts with general M‐N‐C structures, here, it is proved that a coordinated O atom can also play a significant role in tuning the intrinsic catalytic activities of transition metals. The biomimetic electrocatalyst exhibits superior performance for the ORR and zinc–air batteries under alkaline conditions, which is even better than that of commercial Pt/C. The excellent performance can be ascribed to the abundant atomically dispersed Mn cofactors in the graphene frameworks, confirmed by various characterization methods. Theoretical calculations reveal that the intrinsic catalytic activity of metal Mn can be significantly improved via changing local geometry of nearest coordinated O and N atoms. Especially, graphene frameworks containing the Mn‐N₃O₁ cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state.     

Co Nanoparticles Confined in 3D Nitrogen‐Doped Porous Carbon Foams as Bifunctional Electrocatalysts for Long‐Life Rechargeable Zn–Air Batteries

Proper design and simple preparation of nonnoble bifunctional electrocatalysts with high cost performance and strong durability for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is highly demanded but still full of enormous challenges. In this work, a spontaneous gas‐foaming strategy is presented to synthesize cobalt nanoparticles confined in 3D nitrogen‐doped porous carbon foams (CoNCF) by simply carbonizing the mixture of citric acid, NH₄Cl, and Co(NO₃)₂·6H₂O. Thanks to its particular 3D porous foam architecture, ultrahigh specific surface area (1641 m² g^?1), and homogeneous distribution of active sites (C–N, Co–N_x, and Co–O moieties), the optimized CoNCF‐1000‐80 (carbonized at 1000 °C, containing 80 mg Co(NO₃)₂·6H₂O in precursors) catalyst exhibits a remarkable bifunctional activity and long‐term durability toward both ORR and OER. Its bifunctional activity parameter (ΔE) is as low as 0.84 V, which is much smaller than that of noble metal catalyst and comparable to state‐of‐the‐art bifunctional catalysts. When worked as an air electrode catalyst in rechargeable Zn–air batteries, a high energy density (797 Wh kg^?1), a low charge/discharge voltage gap (0.75 V), and a long‐term cycle stability (over 166 h) are achieved at 10 mA cm^?2.     

A Hydrangea‐Like Superstructure of Open Carbon Cages with Hierarchical Porosity and Highly Active Metal Sites

Carbon micro‐/nanocages have attracted great attention owing to their wide potential applications. Herein, a self‐templated strategy is presented for the synthesis of a hydrangea‐like superstructure of open carbon cages through morphology‐controlled thermal transformation of core@shell metal–organic frameworks (MOFs). Direct pyrolysis of core@shell zinc (Zn)@cobalt (Co)‐MOFs produces well‐defined open‐wall nitrogen‐doped carbon cages. By introducing guest iron (Fe) ions into the core@shell MOF precursor, the open carbon cages are self‐assembled into a hydrangea‐like 3D superstructure interconnected by carbon nanotubes, which are grown in situ on the Fe–Co alloy nanoparticles formed during the pyrolysis of Fe‐introduced Zn@Co‐MOFs. Taking advantage of such hierarchically porous superstructures with excellent accessibility, synergetic effects between the Fe and the Co, and the presence of catalytically active sites of both metal nanoparticles and metal–N_x species, this superstructure of open carbon cages exhibits efficient bifunctional catalysis for both oxygen evolution reaction and oxygen reduction reaction, achieving a great performance in Zn–air batteries.     

“Wiring” Fe‐Nx‐Embedded Porous Carbon Framework onto 1D Nanotubes for Efficient Oxygen Reduction Reaction in Alkaline and Acidic Media

This study presents a novel metal‐organic‐framework‐engaged synthesis route based on porous tellurium nanotubes as a sacrificial template for hierarchically porous 1D carbon nanotubes. Furthermore, an ultrathin Fe‐ion‐containing polydopamine layer has been introduced to generate highly effective FeN_xC active sites into the carbon framework and to induce a high degree of graphitization. The synergistic effects between the hierarchically porous 1D carbon structure and the embedded FeN_xC active sites in the carbon framework manifest in superior catalytic activity toward oxygen reduction reaction (ORR) compared to Pt/C catalyst in both alkaline and acidic media. A rechargeable zinc‐air battery assembled in a decoupled configuration with the nonprecious pCNT@Fe@GL/CNF ORR electrode and Ni‐Fe LDH/NiF oxygen evolution reaction (OER) electrode exhibits charge–discharge overpotentials similar to the counterparts of Pt/C ORR electrode and IrO₂ OER electrode.     

Defect Engineering toward Atomic Co–Nx–C in Hierarchical Graphene for Rechargeable Flexible Solid Zn‐Air Batteries

Rechargeable flexible solid Zn‐air battery, with a high theoretical energy density of 1086 Wh kg^?1, is among the most attractive energy technologies for future flexible and wearable electronics; nevertheless, the practical application is greatly hindered by the sluggish oxygen reduction reaction/oxygen evolution reaction (ORR/OER) kinetics on the air electrode. Precious metal‐free functionalized carbon materials are widely demonstrated as the most promising candidates, while it still lacks effective synthetic methodology to controllably synthesize carbocatalysts with targeted active sites. This work demonstrates the direct utilization of the intrinsic structural defects in nanocarbon to generate atomically dispersed Co–N_x–C active sites via defect engineering. As‐fabricated Co/N/O tri‐doped graphene catalysts with highly active sites and hierarchical porous scaffolds exhibit superior ORR/OER bifunctional activities and impressive applications in rechargeable Zn‐air batteries. Specifically, when integrated into a rechargeable and flexible solid Zn‐air battery, a high open‐circuit voltage of 1.44 V, a stable discharge voltage of 1.19 V, and a high energy efficiency of 63% at 1.0 mA cm^?2 are achieved even under bending. The defect engineering strategy provides a new concept and effective methodology for the full utilization of nanocarbon materials with various structural features and further development of advanced energy materials.     

Atomic‐Level Fe‐N‐C Coupled with Fe3C‐Fe Nanocomposites in Carbon Matrixes as High‐Efficiency Bifunctional Oxygen Catalysts

Highly active and durable bifunctional oxygen electrocatalysts are of pivotal importance for clean and renewable energy conversion devices, but the lack of earth‐abundant electrocatalysts to improve the intrinsic sluggish kinetic process of oxygen reduction/evolution reactions (ORR/OER) is still a challenge. Fe‐N‐C catalysts with abundant natural merits are considered as promising alternatives to noble‐based catalysts, yet further improvements are urgently needed because of their poor stability and unclear catalytic mechanism. Here, an atomic‐level Fe‐N‐C electrocatalyst coupled with low crystalline Fe₃C‐Fe nanocomposite in 3D carbon matrix (Fe‐SAs/Fe₃C‐Fe@NC) is fabricated by a facile and scalable method. Versus atomically FeN_x species and crystallized Fe₃C‐Fe nanoparticles, Fe‐SAs/Fe₃C‐Fe@NC catalyst, abundant in vertical branched carbon nanotubes decorated on intertwined carbon nanofibers, exhibits high electrocatalytic activities and excellent stabilities both in ORR (E_1/2, 0.927 V) and OER (E_J=10, 1.57 V). This performance benefits from the strong synergistic effects of multicomponents and the unique structural advantages. In‐depth X‐ray absorption fine structure analysis and density functional theory calculation further demonstrate that more extra charges derived from modified Fe clusters decisively promote the ORR/OER performance for atomically FeN₄ configurations by enhanced oxygen adsorption energy. These insightful findings inspire new perspectives for the rational design and synthesis of economical–practical bifunctional oxygen electrocatalysts.     

Sustainable Synthesis of Co@NC Core Shell Nanostructures from Metal Organic Frameworks via Mechanochemical Coordination Self‐Assembly: An Efficient Electrocatalyst for Oxygen Reduction Reaction

Herein, a new type of cobalt encapsulated nitrogen‐doped carbon (Co@NC) nanostructure employing Zn_xCo_1?x(C₃H₄N₂) metal–organic framework (MOF) as precursor is developed, by a simple, ecofriendly, solvent‐free approach that utilizes a mechanochemical coordination self‐assembly strategy. Possible evolution of Zn_xCo_1?x(C₃H₄N₂) MOF structures and their conversion to Co@NC nanostructures is established from an X‐ray diffraction technique and transmission electron microscopy analysis, which reveal that MOF‐derived Co@NC core–shell nanostructures are well ordered and highly crystalline in nature. Co@NC–MOF core–shell nanostructures show excellent catalytic activity for the oxygen reduction reaction (ORR), with onset potential of 0.97 V and half‐wave potential of 0.88 V versus relative hydrogen electrode in alkaline electrolyte, and excellent durability with zero degradation after 5000 potential cycles; whereas under similar experimental conditions, the commonly utilized Pt/C electrocatalyst degrades. The Co@NC–MOF electrocatalyst also shows excellent tolerance to methanol, unlike the Pt/C electrocatalyst. X‐ray photoelectron spectroscopy (XPS) analysis shows the presence of ORR active pyridinic‐N and graphitic‐N species, along with CoN_x? C_y and Co? N_x ORR active (M–N–C) sites. Enhanced electron transfer kinetics from nitrogen‐doped carbon shell to core Co nanoparticles, the existence of M–N–C active sites, and protective NC shells are responsible for high ORR activity and durability of the Co@NC–MOF electrocatalyst.     

An Oxygen‐Vacancy‐Rich Semiconductor‐Supported Bifunctional Catalyst for Efficient and Stable Zinc–Air Batteries

The highly oxidative operating conditions of rechargeable zinc–air batteries causes significant carbon‐support corrosion of bifunctional oxygen electrocatalysts. Here, a new strategy for the catalyst support design focusing on oxygen vacancy (OV)‐rich, low‐bandgap semiconductor is proposed. The OVs promote the electrical conductivity of the oxide support, and at the same time offer a strong metal–support interaction (SMSI), which enables the catalysts to have small metal size, high catalytic activity, and high stability. The strategy is demonstrated by successfully synthesizing ultrafine Co‐metal‐decorated 3D ordered macroporous titanium oxynitride (3DOM‐Co@TiO_xN_y). The 3DOM‐Co@TiO_xN_y catalyst exhibits comparable activities for oxygen reduction and evolution reactions, but much higher cycling stability than noble metals in alkaline conditions. The zinc–air battery using this catalyst delivers an excellent stability with less than 1% energy efficiency loss over 900 charge–discharge cycles at 20 mA cm^?2. The high stability is attributed to the strong SMSI between Co and 3DOM‐TiO_xN_y which is verified by density functional theory calculations. This work sheds light on using OV‐rich semiconductors as a promising support to design efficient and durable nonprecious electrocatalysts.     

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.     

Exceptional Performance of Hierarchical Ni–Fe (hydr)oxide@NiCu Electrocatalysts for Water Splitting

Developing low‐cost bifunctional electrocatalysts with superior activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of great importance for the widespread application of the water splitting technique. In this work, using earth‐abundant transition metals (i.e., nickel, iron, and copper), 3D hierarchical nanoarchitectures, consisting of ultrathin Ni–Fe layered‐double‐hydroxide (Ni–Fe LDH) nanosheets or porous Ni–Fe oxides (NiFeO_x) assembled to a metallic NiCu alloy, are delicately constructed. In alkaline solution, the as‐prepared Ni–Fe LDH@NiCu possesses outstanding OER activity, achieving a current density of 10 mA cm^?2 at an overpotential of 218 mV, which is smaller than that of RuO₂ catalyst (249 mV). In contrast, the resulting NiFeO_x@NiCu exhibits better HER activity, yielding a current density of 10 mA cm^?2 at an overpotential of 66 mV, which is slightly higher than that of Pt catalyst (53 mV) but superior to all other transition metal (hydr)oxide‐based electrocatalysts. The remarkable activity of the Ni–Fe LDH@NiCu and NiFeO_x@NiCu is further demonstrated by a 1.5 V solar‐panel‐powered electrolyzer, resulting in current densities of 10 and 50 mA cm^?2 at overpotentials of 293 and 506 mV, respectively. Such performance renders the as‐prepared materials as the best bifunctional electrocatalysts so far.     

Nitrogen‐Doped Carbon Nanotube Confined Co–Nx Sites for Selective Hydrogenation of Biomass‐Derived Compounds

Biomass is the most abundant renewable resource on earth and developing high‐performance nonprecious selective hydrogenation (SH) catalysts will enable the use of biomass to replace rapidly diminishing fossil resources. This work utilizes ZIF‐67‐derived nitrogen‐doped carbon nanotubes to confine Co nanoparticles (NPs) with Co–N_x active sites as a high‐performance SH catalyst. The confined Co NPs with Co–N_x exhibit excellent catalytic activity, selectivity, and stability toward a wide range of biomass‐derived compounds. Such active sites can selectively hydrogenate aldehyde, ketone, carboxyl, and nitro groups of biomass‐derived compounds into value‐added fine chemicals with 100% selectivity. The reported approach could be adopted to create other forms of catalytically active sites from other nonprecious metals.     

Atomic Fe–Nx Coupled Open‐Mesoporous Carbon Nanofibers for Efficient and Bioadaptable Oxygen Electrode in Mg–Air Batteries

The recently emerging metal–air batteries equipped with advanced oxygen electrodes have provided enormous opportunities to develop the next generation of wearable and bio‐adaptable power sources. Theoretically, neutral electrolyte‐based Mg–air batteries possess potential advantages in electronics and biomedical applications over the other metal–air counterparts, especially the alkaline‐based Zn–air batteries. However, the rational design of advanced oxygen electrode for Mg–air batteries with high discharge voltage and capacity under neutral conditions still remains a major challenge. Inspired by fibrous string structures of bufo‐spawn, it is reported here that the scalable synthesis of atomic Fe–N_x coupled open‐mesoporous N‐doped‐carbon nanofibers (OM‐NCNF‐FeN_x) as advanced oxygen electrode for Mg–air batteries. The fabricated OM‐NCNF‐FeN_x electrodes present manifold advantages, including open‐mesoporous and interconnected structures, 3D hierarchically porous networks, good bio‐adaptability, homogeneously coupled atomic Fe–N_x sites, and high oxygen electrocatalytic performances. Most importantly, the assembled Mg–air batteries with neutral electrolytes reveal high open‐circuit voltage, stable discharge voltage plateaus, high capacity, long operating life, and good flexibility. Overall, the discovery on fabricating atomic OM‐NCNF‐FeN_x electrode will not only create new pathways for achieving flexible, wearable, and bio‐adaptable power sources, but also take a step towards the scale‐up production of advanced nanofibrous carbon electrodes for a broad range of applications.     

Reduced Graphene Oxide‐Wrapped Co9–xFexS8/Co,Fe‐N‐C Composite as Bifunctional Electrocatalyst for Oxygen Reduction and Evolution

Searching for highly efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) using nonnoble metal‐based catalysts is essential for the development of many energy conversion systems, including rechargeable fuel cells and metal–air batteries. Here, Co_9–xFe_xS₈/Co,Fe‐N‐C hybrids wrapped by reduced graphene oxide (rGO) (abbreviated as S‐Co_9–xFe_xS₈@rGO) are synthesized through a semivulcanization and calcination method using graphene oxide (GO) wrapped bimetallic zeolite imidazolate framework (ZIF) Co,Fe‐ZIF (CoFe‐ZIF@GO) as precursors. Benefiting from the synergistic effect of OER active CoFeS and ORR active Co,Fe‐N‐C in a single component, as well as high dispersity and enhanced conductivity derived from rGO coating and Fe‐doping, the obtained S‐Co_9–xFe_xS₈@rGO‐10 catalyst shows an ultrasmall overpotential of ≈0.29 V at 10 mA cm^?2 in OER and a half‐wave potential of 0.84 V in ORR, combining a superior oxygen electrode activity of ≈0.68 V in 0.1 m KOH.     

Ionic Exchange of Metal−Organic Frameworks for Constructing Unsaturated Copper Single‐Atom Catalysts for Boosting Oxygen Reduction Reaction

Regulating the coordination environment of atomically dispersed catalysts is vital for catalytic reaction but still remains a challenge. Herein, an ionic exchange strategy is developed to fabricate atomically dispersed copper (Cu) catalysts with controllable coordination structure. In this process, the adsorbed Cu ions exchange with Zn nodes in ZIF‐8 under high temperature, resulting in the trapping of Cu atoms within the cavities of the metal?organic framework, and thus forming Cu single‐atom catalysts. More importantly, altering pyrolysis temperature can effectively control the structure of active metal center at atomic level. Specifically, higher treatment temperature (900 °C) leads to unsaturated Cu–nitrogen architecture (Cu? N₃ moieties) in atomically dispersed Cu catalysts. Electrochemical test indicates atomically dispersed Cu catalysts with Cu? N₃ moieties possess superior oxygen reduction reaction performance than that with higher Cu–nitrogen coordination number (Cu? N₄ moieties), with a higher half‐wave potential of 180 mV and the 10 times turnover frequency than that of CuN₄. Density functional theory calculation analysis further shows that the low N coordination number of Cu single‐atom catalysts (Cu? N₃) is favorable for the formation of O₂* intermediate, and thus boosts the oxygen reduction reaction.     

Porous Cobalt–Nickel Hydroxide Nanosheets with Active Cobalt Ions for Overall Water Splitting

Low‐cost and high‐performance catalysts are of great significance for electrochemical water splitting. Here, it is reported that a laser‐synthesized catalyst, porous Co_0.75Ni_0.25(OH)₂ nanosheets, is highly active for catalyzing overall water splitting. The porous nanosheets exhibit low overpotentials for hydrogen evolution reaction (95 mV@10 mA cm^?2) and oxygen evolution reaction (235 mV@10 mA cm^?2). As both anode and cathode catalysts, the porous nanosheets achieve a current density of 10 mA cm^?2 at an external voltage of 1.56 V, which is much lower than that of commercial Ir/C‐Pt/C couple (1.62 V). Experimental and theoretical investigations reveal that numerous Co³⁺ ions are generated on the pore wall of nanosheets, and the unique atomic structure around Co³⁺ ions leads to appropriate electronic structure and adsorption energy of intermediates, thus accelerating hydrogen and oxygen evolution.     

Synthesis of Bimetallic Conductive 2D Metal–Organic Framework (CoxNiy‐CAT) and Its Mass Production: Enhanced Electrochemical Oxygen Reduction Activity

The development of new electrocatalysts for electrochemical oxygen reduction to replace expensive and rare platinum‐based catalysts is an important issue in energy storage and conversion research. In this context, conductive and porous metal–organic frameworks (MOFs) are considered promising materials for the oxygen reduction reaction (ORR) due to not only their high surface area and well‐developed pores but also versatile structural features and chemical compositions. Herein, the preparation of bimetallic conductive 2D MOFs (Co_xNi_y‐CATs) are reported for use as catalysts in the ORR. The ratio of the two metal ions (Co²⁺ and Ni²⁺) in the bimetallic Co_xNi_y‐CATs is rationally controlled to determine the optimal composition of Co_xNi_y‐CAT for efficient performance in the ORR. Indeed, bimetallic MOFs display enhanced ORR activity compared to their monometallic counterparts (Co‐CAT or Ni‐CAT). During the ORR, bimetallic Co_xNi_y‐CATs retain an advantageous characteristic of Co‐CAT in relation to its high diffusion‐limiting current density, as well as a key advantage of Ni‐CAT in relation to its high onset potential. Moreover, the ORR‐active bimetallic Co_xNi_y‐CAT with excellent ORR activity is prepared at a large scale via a convenient method using a ball‐mill reactor.