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.     

On the Role of Metals in Nitrogen‐Doped Carbon Electrocatalysts for Oxygen Reduction

The notion of metal‐free catalysts is used to refer to carbon materials modified with nonmetallic elements. However, some claimed metal‐free catalysts are prepared using metal‐containing precursors. It is highly contested that metal residues in nitrogen‐doped carbon (NC) catalysts play a crucial role in the oxygen reduction reaction (ORR). In an attempt to reconcile divergent views, a definition for truly metal‐free catalysts is proposed and the differences between NC and M‐N_x/C catalysts are discussed. Metal impurities at levels usually undetectable by techniques such as XPS, XRD, and EDX significantly promote the ORR. Poisoning tests to mask the metal ions reveal the involvement of metal residues as active sites or as modifiers of the electronic structure of the active sites in NC. The unique merits of both M‐N_x/C and NC catalysts are discussed to inspire the development of more advanced nonprecious‐metal catalysts for the ORR.     

Bamboo‐Like Nitrogen‐Doped Carbon Nanotubes with Co Nanoparticles Encapsulated at the Tips: Uniform and Large‐Scale Synthesis and High‐Performance Electrocatalysts for Oxygen Reduction

In recent years, various non‐precious metal electrocatalysts for the oxygen reduction reaction (ORR) have been extensively investigated. The development of an efficient and simple method to synthesize non‐precious metal catalysts with ORR activity superior to that of Pt is extremely significant for large‐scale applications of fuel cells. Here, we develop a facile, low‐cost, and large‐scale synthesis method for uniform nitrogen‐doped (N‐doped) bamboo‐like CNTs (NBCNT) with Co nanoparticles encapsulated at the tips by annealing a mixture of cobalt acetate and melamine. The uniform NBCNT shows better ORR catalytic activity and higher stability in alkaline solutions as compared with commercial Pt/C and comparable catalytic activity to Pt/C in acidic media. NBCNTs exhibit outstanding ORR catalytic activity due to high defect density, uniform bamboo‐like structure, and the synergistic effect between the Co nanoparticles and protective graphitic layers. This facile method to synthesize catalysts, which is amenable to the large‐scale commercialization of fuel cells, will open a new avenue for the development of low‐cost and high‐performance ORR catalysts to replace Pt‐based catalysts for applications in energy conversion.     

Nitrogen‐Doped Carbon Nanosheets with Size‐Defined Mesopores as Highly Efficient Metal‐Free Catalyst for the Oxygen Reduction Reaction

Nitrogen‐doped carbon nanosheets (NDCN) with size‐defined mesopores are reported as highly efficient metal‐free catalyst for the oxygen reduction reaction (ORR). A uniform and tunable mesoporous structure of NDCN is prepared using a templating approach. Such controlled mesoporous structure in the NDCN exerts an essential influence on the electrocatalytic performance in both alkaline and acidic media for the ORR. The NDCN catalyst with a pore diameter of 22 nm exhibits a more positive ORR onset potential than that of Pt/C (?0.01 V vs. ?0.02 V) and a high diffusion‐limited current approaching that of Pt/C (5.45 vs. 5.78 mA cm^?2) in alkaline medium. Moreover, the catalyst shows pronounced electrocatalytic activity and long‐term stability towards the ORR under acidic conditions. The unique planar mesoporous shells of the NDCN provide exposed highly electroactive and stable catalytic sites, which boost the electrocatalytic activity of metal‐free NDCN catalyst.     

Synthesis,Characterization, and Application of Metal Nanoparticles Supported on Nitrogen‐Doped Carbon: Catalysis beyond Electrochemistry

Metal nanoparticles deposited on N‐doped carbon materials have emerged as novel catalysts for various organic transformations. In this Minireview, strategies for the synthesis of metal composites on N‐doped carbon supports and their state‐of‐the‐art characterization are briefly described. The catalytic application of these fascinating materials in several industrially relevant reactions, including oxidations, hydrogenations, Fischer–Tropsch syntheses, and H₂ generation, is also summarized. Furthermore, the effects of nitrogen incorporation on the different catalytic systems are highlighted.     

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.     

Ionic Liquids as Precursors for Efficient Mesoporous Iron‐Nitrogen‐Doped Oxygen Reduction Electrocatalysts

A ferrocene‐based ionic liquid (Fe‐IL) is used as a metal‐containing feedstock with a nitrogen‐enriched ionic liquid (N‐IL) as a compatible nitrogen content modulator to prepare a novel type of non‐precious‐metal–nitrogen–carbon (M‐N‐C) catalysts, which feature ordered mesoporous structure consisting of uniform iron oxide nanoparticles embedded into N‐enriched carbons. The catalyst Fe¹⁰@NOMC exhibits comparable catalytic activity but superior long‐term stability to 20 wt % Pt/C for ORR with four‐electron transfer pathway under alkaline conditions. Such outstanding catalytic performance is ascribed to the populated Fe (Fe₃O₄) and N (N2) active sites with synergetic chemical coupling as well as the ordered mesoporous structure and high surface area endowed by both the versatile precursors and the synthetic strategy, which also open new avenues for the development of M‐N‐C catalytic materials.     

Iron Carbide Nanoparticles Encapsulated in Mesoporous Fe‐N‐Doped Carbon Nanofibers for Efficient Electrocatalysis

Exploring low‐cost and high‐performance nonprecious metal catalysts (NPMCs) for oxygen reduction reaction (ORR) in fuel cells and metal–air batteries is crucial for the commercialization of these energy conversion and storage devices. Here we report a novel NPMC consisting of Fe₃C nanoparticles encapsulated in mesoporous Fe‐N‐doped carbon nanofibers, which is synthesized by a cost‐effective method using carbonaceous nanofibers, pyrrole, and FeCl₃ as precursors. The electrocatalyst exhibits outstanding ORR activity (onset potential of ?0.02 V and half‐wave potential of ?0.140 V) closely comparable to the state‐of‐the‐art Pt/C catalyst in alkaline media, and good ORR activity in acidic media, which is among the highest reported activities of NPMCs.     

High Performance Oxide Functionalized Nitrogen‐Doped Mesocellular Carbon Foam for Biosensor Construction

Nitrogen‐doped mesocellular carbon foam (denoted as MCF? CN_x) with high surface area and large pore volume was prepared and characterized in detail. The MCF? CN_x was further functionalized by oxidation with HNO₃ (denoted as MCF? CN_x‐O) in order to effectively improve its hydrophilicity and biocompatibility. Both MCF? CN_x and MCF? CN_x‐O were used for immobilization of Hb and design of electrochemical biosensors. The activity of Hb immobilized on MCF? CN_x‐O is two times higher than that of Hb immobilized on MCF? CN_x. The Hb‐MCF? CN_x‐O‐Nafion modified electrode displays fast response, high sensitivity and low detection limit to the detection of hydrogen peroxide. The sensitivity of Hb‐MCF? CN_x‐O‐Nafion modified electrode (477 μA mM^?1 cm^?2) is twice that of Hb‐MCF? CN_x‐Nafion modified electrode.     

Atomically Dispersed Nickel(I) on an Alloy‐Encapsulated Nitrogen‐Doped Carbon Nanotube Array for High‐Performance Electrochemical CO2 Reduction Reaction

Single‐atom catalysts (SACs) show great promise for electrochemical CO₂ reduction reaction (CRR), but the low density of active sites and the poor electrical conduction and mass transport of the single‐atom electrode greatly limit their performance. Herein, we prepared a nickel single‐atom electrode consisting of isolated, high‐density and low‐valent nickel(I) sites anchored on a self‐standing N‐doped carbon nanotube array with nickel–copper alloy encapsulation on a carbon‐fiber paper. The combination of single‐atom nickel(I) sites and self‐standing array structure gives rise to an excellent electrocatalytic CO₂ reduction performance. The introduction of copper tunes the d‐band electron configuration and enhances the adsorption of hydrogen, which impedes the hydrogen evolution reaction. The single‐nickel‐atom electrode exhibits a specific current density of ?32.87 mA cm^?2 and turnover frequency of 1962 h^?1 at a mild overpotential of 620 mV for CO formation with 97 % Faradic efficiency.     

Identification of Catalytic Sites for Oxygen Reduction in Metal/Nitrogen‐Doped Carbons with Encapsulated Metal Nanoparticles

The development of metal‐N‐C materials as efficient non‐precious metal (NPM) catalysts for catalysing the oxygen reduction reaction (ORR) as alternatives to platinum is important for the practical use of proton exchange membrane fuel cells (PEMFCs). However, metal‐N‐C materials have high structural heterogeneity. As a result of their high‐temperature synthesis they often consist of metal‐N_x sites and graphene‐encapsulated metal nanoparticles. Thus it is hard to identify the active structure of metal‐N‐C catalysts. Herein, we report a low‐temperature NH₄Cl‐treatment to etch out graphene‐encapsulated nanoparticles from metal‐N‐C catalysts without destruction of co‐existing atomically dispersed metal‐N_x sites. Catalytic activity is much enhanced by this selective removal of metallic nanoparticles. Accordingly, we can confirm the spectator role of graphene‐encapsulated nanoparticles and the pivotal role of metal‐N_x sites in the metal‐N‐C materials for ORR in the acidic medium.     

Cu Nanoparticles Embedded in N‐Doped Carbon Materials for Oxygen Reduction Reaction

Development of eco‐friendly, cost‐effective, and high‐performance electrocatalysts to replace precious metal platinum for oxygen reduction reaction (ORR) has received increasing attention. Herein, we adopt a facile one‐pot strategy to embed Cu nanoparticles onto N‐doped carbon‐graphene (Cu@NC‐700). The Cu@NC‐700 exhibits robust and efficient ORR catalysis with positive half‐wave potential (~0.86 V vs. RHE) and low Tafel slope (33.9 mV?dec^–1) in 0.1 M KOH solution. Meanwhile, it manifests remarkable electrochemical stability, and strong tolerance to methanol crossover and carbon monoxide poisoning. The synergistic effect between Cu‐N‐C sites, Cu nanoparticles, and N‐doped carbon support speeds up ORR electrocatalysis.     

A Template‐Free Method for Preparation of Cobalt Nanoparticles Embedded in N‐Doped Carbon Nanofibers with a Hierarchical Pore Structure for Oxygen Reduction

Designing and preparing porous materials without using any templates is a challenge. Herein, single‐nozzle electrospinning technology coupled with post pyrolysis is applied to prepare cobalt nanoparticles embedded in N‐doped carbon nanofibers with a hierarchical pore structure (HP‐Co‐NCNFs). The resultant HP‐Co‐NCNFs have lengths up to several millimeters with an average diameter of 200 nm and possess abundant micro/meso/macropores on both the surface and within the fibers. Such a microstructure endows the surface area as high as 115 m² g^?1. When used as an electrocatalyst for the oxygen reduction reaction (ORR), the HP‐Co‐NCNFs exhibit outstanding electrochemical performance in terms of activity, methanol tolerance, and durability. The hierarchically porous structure and high surface area can effectively decrease the mass transport resistance and increase the exposed ORR active sites. The sufficient amount of exposed ORR active sites along with accessible transport channel and enhanced electrical conductivity may be responsible for the good electrocatalytic performance.     

Nitrogen‐Doped Carbon Nanomaterials: Synthesis,Characteristics and Applications

Nonmetallic carbon‐based nanomaterials (CNMs) are important in various potential applications, especially after the emergence of graphene and carbon nanotubes, which demonstrate outstanding properties arising from their unique nanostructures. The pristine graphitic structure of CNMs consists of sp² hybrid C?C bonds and is considered to be neutral in nature with low wettability and poor reactivity. To improve its compatibility with other materials and, hence, for greater applicability, CNMs are generally required to be functionalized effectively and/or doped with heteroatoms in their graphitic frameworks for feasible interfacial interactions. Among the various possible functional/doping elements, nitrogen (N) atoms have received much attention given their potential to fine tune the intrinsic properties, such as the work‐function, charge carrier concentration, surface energy, and polarization, of CNMs. N‐doping improves the surface energy and reactivity with enhanced charge polarization and minimal damage to carbon frameworks. The modified surface energy and chemical activity of N‐doped carbon nanomaterials (NCNMs) can be useful for a broad range of applications, including fuel cells, solar cells, Li‐ion batteries, supercapacitors, chemical catalysts, catalyst supports, and so forth.