ZIF‐8 Derived Graphene‐Based Nitrogen‐Doped Porous Carbon Sheets as Highly Efficient and Durable Oxygen Reduction Electrocatalysts

Nitrogen‐doped carbon (NC) materials have been proposed as next‐generation oxygen reduction reaction (ORR) catalysts to significantly improve scalability and reduce costs, but these alternatives usually exhibit low activity and/or gradual deactivation during use. Here, we develop new 2D sandwich‐like zeolitic imidazolate framework (ZIF) derived graphene‐based nitrogen‐doped porous carbon sheets (GNPCSs) obtained by in situ growing ZIF on graphene oxide (GO). Compared to commercial Pt/C catalyst, the GNPCSs show comparable onset potential, higher current density, and especially an excellent tolerance to methanol and superior durability in the ORR. Those properties might be attributed to a synergistic effect between NC and graphene with regard to structure and composition. Furthermore, higher open‐circuit voltage and power density are obtained in direct methanol fuel cells.     

A Universal and Facile Way for the Development of Superior Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions Utilizing the Synergistic Effect

Increasing energy demands have stimulated intense research activities on reversible electrochemical conversion and storage systems with high efficiency, low cost, and environmental benignity. It is highly challenging but desirable to develop efficient bifunctional catalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A universal and facile method for the development of bifunctional electrocatalysts with outstanding electrocatalytic activity for both the ORR and OER in alkaline medium is reported. A mixture of Pt/C catalyst with superior ORR activity and a perovskite oxide based catalyst with outstanding OER activity was employed in appropriate ratios, and prepared by simple ultrasonic mixing. Nanosized platinum particles with a wide range of platinum to oxide mass ratios was realized easily in this way. The as‐formed Pt/C–oxide composites showed better ORR activity than a single Pt/C catalyst and better OER activity than a single oxide to bring about much improved bifunctionality (ΔE is only ≈0.8 V for Pt/C–BSCF; BSCF=Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ), due to the synergistic effect. The electronic transfer mechanism and the rate‐determining step and spillover mechanism were two possible origins of such a synergistic effect. Additionally, the phenomenon was found to be universal, although the best performance could be reached at different platinum to oxide mass ratios for different oxide catalysts. This work thus provides an innovative strategy for the development of new bifunctional electrocatalysts with wide application potentials in high‐energy and efficient electrochemical energy storage and conversion.     

Co@Co3O4 Encapsulated in Carbon Nanotube‐Grafted Nitrogen‐Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode

Efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are vitally important for various energy conversion devices, such as regenerative fuel cells and metal–air batteries. However, realization of such electrodes is impeded by insufficient activity and instability of electrocatalysts for both water splitting and oxygen reduction. We report highly active bifunctional electrocatalysts for oxygen electrodes comprising core–shell Co@Co₃O₄ nanoparticles embedded in CNT‐grafted N‐doped carbon‐polyhedra obtained by the pyrolysis of cobalt metal–organic framework (ZIF‐67) in a reductive H₂ atmosphere and subsequent controlled oxidative calcination. The catalysts afford 0.85 V reversible overvoltage in 0.1 m KOH, surpassing Pt/C, IrO₂, and RuO₂ and thus ranking them among one of the best non‐precious‐metal electrocatalysts for reversible oxygen electrodes.     

Ni3FeN‐Supported Fe3Pt Intermetallic Nanoalloy as a High‐Performance Bifunctional Catalyst for Metal–Air Batteries

Electrocatalysts for both the oxygen reduction and evolution reactions (ORR and OER) are vital for the performances of rechargeable metal–air batteries. Herein, we report an advanced bifunctional oxygen electrocatalyst consisting of porous metallic nickel‐iron nitride (Ni₃FeN) supporting ordered Fe₃Pt intermetallic nanoalloy. In this hybrid catalyst, the bimetallic nitride Ni₃FeN mainly contributes to the high activity for the OER while the ordered Fe₃Pt nanoalloy contributes to the excellent activity for the ORR. Robust Ni₃FeN‐supported Fe₃Pt catalysts show superior catalytic performance to the state‐of‐the‐art ORR catalyst (Pt/C) and OER catalyst (Ir/C). The Fe₃Pt/Ni₃FeN bifunctional catalyst enables Zn–air batteries to achieve a long‐term cycling performance of over 480 h at 10 mA cm⁻² with high efficiency. The extraordinarily high performance of the Fe₃Pt/Ni₃FeN bifunctional catalyst makes it a very promising air cathode in alkaline electrolyte.     

NiMn‐Based Bimetal–Organic Framework Nanosheets Supported on Multi‐Channel Carbon Fibers for Efficient Oxygen Electrocatalysis

Developing noble‐metal‐free bifunctional oxygen electrocatalysts is of great significance for energy conversion and storage systems. Herein, we have developed a transformation method for growing NiMn‐based bimetal–organic framework (NiMn‐MOF) nanosheets on multi‐channel carbon fibers (MCCF) as a bifunctional oxygen electrocatalyst. Owing to the desired components and architecture, the MCCF/NiMn‐MOFs manifest comparable electrocatalytic performance towards oxygen reduction reaction (ORR) with the commercial Pt/C electrocatalyst and superior performance towards oxygen evolution reaction (OER) to the benchmark RuO₂ electrocatalyst. X‐ray absorption fine structure (XAFS) spectroscopy and density functional theory (DFT) calculations reveal that the strong synergetic effect of adjacent Ni and Mn nodes within MCCF/NiMn‐MOFs effectively promotes the thermodynamic formation of key *O and *OOH intermediates over active NiO₆ centers towards fast ORR and OER kinetics.     

Metal Phthalocyanine‐Porphyrin‐based Conjugated Microporous Polymer‐derived Bifunctional Electrocatalysts for Zn‐Air Batteries

Conjugated microporous polymers (CMPs) as emerging porous materials with diverse structures and tunable building‐units have attracted much attention in the electrochemical field. Herein, we designed phthalocyanine‐porphyrin‐based conjugated microporous polymers as precursors for fabrication of Co, Fe, N tri‐doped graphene composites towards oxygen reduction and evolution reaction (ORR/OER). As expected, the elements cobalt and iron are well dispersed in graphene carbon and interact with the nitrogen sites, thereby providing extra electrocatalytic active sites and enhancing its overall conductivity. Benefiting from its unique design and structure, the obtained catalyst affords a superior bifunctional catalytic activity with a positive onset potential of 0.957 V for ORR, and a low overpotential of 0.36 V for OER. More attractively, the CoFeNG is employed as an air cathode catalyst in Zn‐air batteries, showing a maximum current density of 215 mA cm^?2 and good cycle stability for 20000 s. The rational design of phthalocyanine‐porphyrin‐based derivatives provides a feasible route for the construction of high‐performance ORR/OER catalysts.     

Cobalt‐Doped Perovskite‐Type Oxide LaMnO3 as Bifunctional Oxygen Catalysts for Hybrid Lithium–Oxygen Batteries

Perovskite‐type oxides based on rare‐earth metals containing lanthanum manganate are promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. Perovskite‐type LaMnO₃ shows excellent ORR performance, but poor OER activity. To improve the OER performance of LaMnO₃, the element cobalt is doped into perovskite‐type LaMnO₃ through a sol–gel method followed by a calcination process. To assess electrocatalytic activities for the ORR and OER, a series of LaMn_1?xCo_xO₃ (x=0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) perovskite oxides were synthesized. The results indicate that the amount of doped cobalt has a significant effect on the catalytic performance of LaMn_1?xCo_xO₃. If x=0.3, LaMn_0.7Co_0.3O₃ not only shows a tolerable electrocatalytic activity for the ORR, but also exhibits a great improvement (>200 mV) on the catalytic activity for the OER; this indicates that the doping of cobalt is an effective approach to improve the OER performance of LaMnO₃. Furthermore, the results demonstrate that LaMn_0.7Co_0.3O₃ is a promising cost‐effective bifunctional catalyst with high performance in the ORR and OER for application in hybrid Li?O₂ batteries.     

Ultra‐small and highly dispersed Pd nanoparticles inside the pores of ZIF‐8: Sustainable approach to waste‐minimized Mizoroki–Heck cross‐coupling reaction based on reusable heterogeneous catalyst

The rapid development of nanomaterials, particularly advanced hybrid nanoparticles, has made new opportunities for the design and fabrication of high‐performance metal‐based catalysts. However, generating metal nanoparticles of desired size without aggregation is an important challenge for enhancing the catalytic activity of metal nanoparticles supported in the host matrix. In this work, a hybrid nanoporous material, namely Pd nanoparticles@N‐heterocyclic carbene@ZIF‐8, with a high internal surface area was successfully prepared using a dispersed anionic sulfonated N‐heterocyclic carbene–Pd(II) precursor inside the cavities of zeolitic imidazolate framework (ZIF‐8) using an impregnation approach followed by reduction with NaBH₄. The anionic sulfonated N‐heterocyclic carbene was found to be a superb ligand for the stabilization of Pd nanoparticles in the pores of ZIF‐8. The resulting system was applied to the Mizoroki–Heck cross‐coupling reaction, in which the catalyst showed high catalytic activity under mild reaction conditions.     

Coordination Chemistry of [Co(acac)2] with N‐Doped Graphene: Implications for Oxygen Reduction Reaction Reactivity of Organometallic Co‐O4‐N Species

Hybridization of organometallic complexes with graphene‐based materials can give rise to enhanced catalytic performance. Understanding the chemical structures within hybrid materials is of primary importance. In this work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co^II(acac)₂] (acac=acetylacetonate), with N‐doped graphene‐based materials at room temperature. Experimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt‐containing species is coordinated to heterocyclic groups in N‐doped graphene as well as to its parental acac ligands. The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to a Pt/C catalyst. Based on the chemical structures and ORR experiments, the catalytically active species is identified as a Co‐O₄‐N structure.     

A review of transition metal‐based bifunctional oxygen electrocatalysts

Electrochemical energy storage and conversion devices play a key role in the development of clean, sustainable, and efficient energy systems to meet the sustainable growth of our society. However, challenging issues including the sluggish kinetics of oxygen electrode reactions involving the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are present, limiting the implementation of devices such as metal‐air batteries, water electrolyzers, and regenerative fuel cells. In this review, various monometallic and bimetallic transition metal oxides (TMOs) and hydroxides are summarized in terms of their application for ORR/OER, in which the merits and demerits of various precious metal and carbon‐based metal oxide materials are discussed, with requirements for better electrocatalysts and catalyst support being introduced as well. Following this, different approaches to improve catalytic activity such as the introduction of doping and defects, the manipulation of crystal facets, and the engineering of supports, compositions, and morphologies are summarized in which TMOs with improved ORR/OER catalytic activities can be synthesized, further improving the speed, stability, and polarization of electrochemical energy storage and conversion devices. Finally, perspectives into the improvement of performance and the better understanding of ORR/OER mechanisms for bifunctional electrocatalysts using in situ spectroscopic techniques and density functional theory calculations are also discussed.     

氧还原和析氧反应的双功能电催化剂--氮磷共掺碳负载四氧化三钴

金属-空气电池具备诸多优势,譬如绿色环保、能量转化率高、启动快速、能量密度高、使用寿命和干态存储时间长等.与燃料电池相比,金属-空气电池结构简单,放电电压平稳,成本低,但依然存在一些制约发展的问题,如阴极催化剂.阴极催化剂在金属-空气电池中发挥催化氧还原反应(oxygen reduction reaction, ORR)和析氧反应(oxygen evolution reac-tion, OER)的关键作用.铂及其合金常用作 ORR的单功能催化剂,而钌和铱等是目前 OER催化效率最高的,但 ORR活性很低,因此需要开发出一种廉价而又具备双功能催化作用的催化剂.单异原子掺杂的碳基催化剂的研究集中在 ORR催化性能上,而多异原子共掺碳最近有研究表明具有双催化氧的性质,如氮磷共掺碳.在这些氮磷共掺的碳架中,氮磷共掺物起着 OER催化作用,掺氮物为 ORR催化的活性位点,而掺磷物起着强化作用.异原子掺杂负载的钴基催化剂(如掺氮还原氧化石墨烯载 Co3O4)是近年来双功能催化剂研究的另一个热点.钴基催化剂有着催化 ORR和 OER的多价价态,然而其本身导电性能差,这一缺陷可通过杂化石墨化碳来弥补,石墨化碳有着优良的导电性能.据我们所知,目前仍没有关于氮磷共掺碳负载的 Co3O4双催化氧的研究.我们合成了氮磷共掺碳(NPC)负载的 Co3O4(Co3O4/NPC),并首次探索了其氧还原和析氧性能. Co3O4/NPC合成分两步进行.首先通过三聚氰胺与植酸之间的酯化或缩聚覆盖在导电炭黑颗粒表面,在保护气氛下焙烧得到 NPC,然后经溶剂热反应以及空气中氧化合成 Co3O4/NPC.催化剂的性能综合考虑了催化活性和稳定性两方面.采用线性扫描伏安法评估了 OER和 ORR的催化活性.对于 OER, Co3O4/NPC的起始电势是0.54 V (以饱和甘汞电极为参比电极),在0.80 V时电流密度达到21.95 mA/cm2,均优于 Co3O4/C和 NPC. Co3O4/NPC的高效 OER催化可归因于氮磷共掺物与 Co3O4之间的协同作用.对于 ORR, Co3O4/NPC的催化效率与商用 Pt/C相近,它们的扩散极限电流密度分别为–4.49和–4.76 mA/cm2(E =–0.80 V).在 ORR过程中, Co3O4起到主要的催化作用.采用计时电流(电流-时间)法评估了催化剂的稳定性.经6 h测定,对于 OER, Co3O4/NPC剩46%电流;而对于 ORR,剩95%电流.整体而言, Co3O4/NPC在 OER和 ORR中都表现出高的催化效率以及良好的稳定性.     

Atomically Dispersed Iron–Nitrogen Species as Electrocatalysts for Bifunctional Oxygen Evolution and Reduction Reactions

Rational design of non‐noble materials as highly efficient, economical, and durable bifunctional catalysts for oxygen evolution and reduction reactions (OER/ORR) is currently a critical obstacle for rechargeable metal‐air batteries. A new route involving S was developed to achieve atomic dispersion of Fe‐N_x species on N and S co‐decorated hierarchical carbon layers, resulting in single‐atom bifunctional OER/ORR catalysts for the first time. The abundant atomically dispersed Fe‐N_x species are highly catalytically active, the hierarchical structure offers more opportunities for active sites, and the electrical conductivity is greatly improved. The obtained electrocatalyst exhibits higher limiting current density and a more positive half‐wave potential for ORR, as well as a lower overpotential for OER under alkaline conditions. Moreover, a rechargeable Zn–air battery device comprising this hybrid catalyst shows superior performance compared to Pt/C catalyst. This work will open a new avenue to design advanced bifunctional catalysts for reversible energy storage and conversion devices.     

Bottom‐Up Fabrication of a Sandwich‐Like Carbon/Graphene Heterostructure with Built‐In FeNC Dopants as Non‐Noble Electrocatalyst for Oxygen Reduction Reaction

High‐performance non‐noble electrocatalysts for oxygen reduction reaction (ORR) are the prerequisite for large‐scale utilization of fuel cells. Herein, a type of sandwiched‐like non‐noble electrocatalyst with highly dispersed FeN_x active sites embedded in a hierarchically porous carbon/graphene heterostructure was fabricated using a bottom‐up strategy. The in situ ion substitution of Fe³⁺ in a nitrogen‐containing MOF (ZIF‐8) allows the Fe‐heteroatoms to be uniformly distributed in the MOF precursor, and the assembly of Fe‐doped ZIF‐8 nano‐crystals with graphene‐oxide and in situ reduction of graphene‐oxide afford a sandwiched‐like Fe‐doped ZIF‐8/graphene heterostructure. This type of heterostructure enables simultaneous optimization of FeN_x active sites, architecture and interface properties for obtaining an electron‐catalyst after a one‐step carbonization. The synergistic effect of these factors render the resulting catalysts with excellent ORR activities. The half‐wave potential of 0.88 V vs. RHE outperforms most of the none‐noble metal catalyst and is comparable with the commercial Pt/C (20 wt %) catalyst. Apart from the high activity, this catalyst exhibits excellent durability and good methanol‐tolerance. Detailed investigations demonstrate that a moderate content of Fe dopants can effectively increase the intrinsic activities, and the hybridization of graphene can enhance the reaction kinetics of ORR. The strategy proposed in this work gives an inspiration towards developing efficient noble‐metal‐free electrocatalysts for ORR.     

Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc–Air Batteries

The lack of high‐efficient, low‐cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc–air batteries. A nanocomposite CoO‐NiO‐NiCo bifunctional electrocatalyst supported by nitrogen‐doped multiwall carbon nanotubes (NCNT/CoO‐NiO‐NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO‐NiO‐NiCo catalysts further demonstrated superior performance to state‐of‐the‐art Pt/C or Pt/C+IrO₂ catalysts in primary and rechargeable zinc–air batteries.     

利用MOF-253衍生氮掺杂碳限域效应促进Pt纳米单晶电催化剂的氧析出反应

目前,为了有效解决电化学能量转化反应动力学过程缓慢和商业化应用等问题,需要大力提高催化剂的电催化活性和稳定性,并大幅降低贵金属催化剂的用量.通常,铂(Pt)基催化剂对燃料电池的氧还原反应(ORR)和水电解过程的氢析出反应(HER)表现出很高的活性.然而,对于高效的金属-空气电池和水电解装置,其中的氧析出反应(OER)则需要高活性的非Pt电催化剂来降低电化学过电位及提高其对高电位的耐受性.虽然相较于Pt催化剂,IrO2和RuO2等贵金属催化剂表现出了更高的OER活性,然而,它们的稳定性差,难以满足实际应用需求,严重阻碍了其在金属-空气电池和水电解中的应用.通常,Pt对OER的低效催化主要归因于在OER电催化过程中Pt与电解液直接接触,导致Pt表面快速被氧化,形成Pt氧化物(Pt^+4O2和Pt^+2O)层.形成的Pt氧化物对OER不起催化作用,从而降低了Pt的利用率和总的水电解效率.为了避免Pt表面的快速氧化,实现高的OER性能,我们将Pt金属纳米粒子有效地限域在超薄功能多孔碳层内.前期,已有大量的有关金属基ORR和HER催化剂研究证明,这种策略对于稳定金属纳米颗粒非常有效,可有效避免金属催化剂的快速氧化,而且还可抑制金属颗粒迁移和团聚;此外,还有利于增强催化剂的导电性和离子物种的扩散能力,从而提高催化剂的电催化性能.然而,要达到提高金属催化剂OER电催化性能的目的,还需要设计一种具有优良结构的功能化异质原子掺杂多孔碳基限域材料.金属有机框架(MOF),特别是MOF-253,由于具有较高的柔韧性、丰富的孔、可控的几何结构和高比表面积,被认为是制备功能多孔碳基限域材料的理想前驱体.为此,通过结合功能多孔碳基材料的限域作用及MOF-253和超细Pt纳米单晶的优势,本文合成了MOF-253衍生氮掺杂碳(N/C)限域的Pt纳米单晶(Pt@N/C)核壳型电催化剂.制备的Pt-N-C框架不仅具有超薄的氮掺杂活性多孔碳保护层壳体(平均厚度为0.51 nm),还有具高度分散和稳定化的Pt纳米单晶核体;值得指出的是,因受到碳层的限域作用,即使经900℃的高温处理,Pt纳米单晶仍保持了较小的晶体尺寸(平均粒径仅为6.7 nm);此外,该催化剂的Pt载量较低,仅为6.1wt%(Pt@N/C-10).将其作为OER电催化剂,表现出优异的OER性能:在10 mA cm^-2电流密度下,其过电位仅为298 mV,低于商业IrO2催化剂(353 mV);而且,经2000周加速电位扫描后,其电位仅降低19.4 mV,也低于IrO2(23.3 mV).本文很好地证明了通过构建空间限域结构可以有效解决Pt等金属催化剂因表面氧化而导致OER动力学活性和稳定性低的问题.     

Pyrolysis of Animal Bones with Vitamin B12: A Facile Route to Efficient Transition Metal–Nitrogen–Carbon (TM‐N‐C) Electrocatalysts for Oxygen Reduction

By pyrolyzing cattle bones, hierarchical porous carbon (HPC) networks with a high surface area (2520 m² g^?1) and connected pores were prepared at a low cost and large scale. Subsequent co‐pyrolysis of HPC with vitamin B12 resulted in the formation of three‐dimensional (3D) hierarchically structured porous cobalt–nitrogen–carbon (Co‐N‐HPC) electrocatalysts with a surface area as high as 859 m² g^?1 as well as a higher oxygen reduction reaction (ORR) electrocatalytic activity, better operation stability, and higher tolerance to methanol than the commercial Pt/C catalyst in alkaline electrolyte.     

Pomegranate‐Inspired Design of Highly Active and Durable Bifunctional Electrocatalysts for Rechargeable Metal–Air Batteries

Rational design of highly active and durable electrocatalysts for oxygen reactions is critical for rechargeable metal–air batteries. Herein, we report the design and development of composite electrocatalysts based on transition metal oxide nanocrystals embedded in a nitrogen‐doped, partially graphitized carbon framework. Benefiting from the unique pomegranate‐like architecture, the composite catalysts possess abundant active sites, strong synergetic coupling, enhanced electron transfer, and high efficiencies in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The Co₃O₄‐based composite electrocatalyst exhibited a high half‐wave potential of 0.842 V for ORR, and a low overpotential of only 450 mV at the current density of 10 mA cm^?2 for OER. A single‐cell zinc–air battery was also fabricated with superior durability, holding great promise in the practical implementation of rechargeable metal–air batteries.     

Carbon‐Based Metal‐Free Catalysts for Electrocatalysis beyond the ORR

Besides their use in fuel cells for energy conversion through the oxygen reduction reaction (ORR), carbon‐based metal‐free catalysts have also been demonstrated to be promising alternatives to noble‐metal/metal oxide catalysts for the oxygen evolution reaction (OER) in metal–air batteries for energy storage and for the splitting of water to produce hydrogen fuels through the hydrogen evolution reaction (HER). This Review focuses on recent progress in the development of carbon‐based metal‐free catalysts for the OER and HER, along with challenges and perspectives in the emerging field of metal‐free electrocatalysis.     

Boosting ORR Catalytic Activity by Integrating Pyridine‐N Dopants,a High Degree of Graphitization,and Hierarchical Pores into a MOF‐Derived N‐Doped Carbon in a Tandem Synthesis

N‐doped carbon materials represent promising metal‐free electrocatalysts for the oxygen reduction reaction (ORR), the cathode reaction in fuel cells, metal–air batteries, and so on. A challenge for optimizing the ORR catalytic activities of these electrocatalysts is to tune their local structures and chemical compositions in a rational and controlled way that can achieve the synergistic function of each factor. Herein, we report a tandem synthetic strategy that integrates multiple contributing factors into an N‐doped carbon. With an N‐containing MOF (ZIF‐8) as the precursor, carbonization at higher temperatures leads to a higher degree of graphitization. Subsequent NH₃ etching of this highly graphitic carbon enabled the introduction of a higher content of pyridine‐N sites and higher porosity. By optimizing these three factors, the resultant carbon materials displayed ORR activity that was far superior to that of carbon derived from a one‐step pyrolysis. The onset potential of 0.955 V versus a reversible hydrogen electrode (RHE) and the half‐wave potential of 0.835 V versus RHE are among the top ranks of metal‐free ORR catalysts and are comparable to commercial Pt/C (20 wt %) catalysts. Kinetic studies revealed lower H₂O₂ yields, higher electron‐transfer numbers, and lower Tafel slopes for these carbon materials compared with that derived from a one‐step carbonization. These findings verify the effectiveness of this tandem synthetic strategy to enhance the ORR activity of N‐doped carbon materials.     

Pyrolytic Carbon‐coated Cu‐Fe Alloy Nanoparticles with High Catalytic Performance for Oxygen Electroreduction

Well‐dispersed carbon‐coated or nitrogen‐doped carbon‐coated copper‐iron alloy nanoparticles (FeCu@C or FeCu@C?N) in carbon‐based supports are obtained using a bimetallic metal‐organic framework (Cu/Fe‐MOF‐74) or a mixture of Cu/Fe‐MOF‐74 and melamine as sacrificial templates and an active‐component precursor by using a pyrolysis method. The investigation results attest formation of Cu?Fe alloy nanoparticles. The obtained FeCu@C catalyst exhibits a catalytic activity with a half‐wave potential of 0.83 V for oxygen reduction reaction (ORR) in alkaline medium, comparable to that on commercial Pt/C catalyst (0.84 V). The catalytic activity of FeCu@C?N for ORR (E_half‐wave=0.87 V) outshines all reported analogues. The excellent performance of FeCu@C?N should be attributed to a change in the energy of the d‐band center of Cu resulting from the formation of the copper–iron alloy, the interaction between alloy nanoparticles and supports and N‐doping in the carbon matrix. Moreover, FeCu@C and FeCu@C?N show better electrochemical stability and methanol tolerance than commercial Pt/C and are expected to be widely used in practical applications.