Oxygen Reduction Reactions on Single‐ or Few‐Atom Discrete Active Sites for Heterogeneous Catalysis

The oxygen reduction reaction (ORR) is of great importance in energy‐converting processes such as fuel cells and in metal–air batteries and is vital to facilitate the transition toward a nonfossil dependent society. The ORR has been associated with expensive noble metal catalysts that facilitate the O₂ adsorption, dissociation, and subsequent electron transfer. Single‐ or few‐atom motifs based on earth‐abundant transition metals, such as Fe, Co, and Mo, combined with nonmetallic elements, such as P, S, and N, embedded in a carbon‐based matrix represent one of the most promising alternatives. Often these are referred to as single atom catalysts; however, the coordination number of the metal atom as well as the type and nearest neighbor configuration has a strong influence on the function of the active sites, and a more adequate term to describe them is metal‐coordinated motifs. Despite intense research, their function and catalytic mechanism still puzzle researchers. They are not molecular systems with discrete energy states; neither can they fully be described by theories that are adapted for heterogeneous bulk catalysts. Here, recent results on single‐ and few‐atom electrocatalyst motifs are reviewed with an emphasis on reports discussing the function and the mechanism of the active sites.     

Highly Active and Stable Graphene Tubes Decorated with FeCoNi Alloy Nanoparticles via a Template‐Free Graphitization for Bifunctional Oxygen Reduction and Evolution

Development of highly active and stable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts from earth‐abundant elements remains a grand challenge for highly demanded reversible fuel cells and metal–air batteries. Carbon catalysts have many advantages over others due to their low cost, excellent electrical conductivity, high surface area, and easy functionalization. However, they typically cannot withstand the highly oxidative OER environment. Here, a new class of bifunctional electrocatalyst is reported, consisting of ultralarge sized nitrogen doped graphene tubes (N‐GTs) (>500 nm) decorated with FeCoNi alloy particles. These tubes are prepared from an inexpensive precursor, dicyandiamide, via a template‐free graphitization process. The ORR/OER activity and the stability of these graphene tube catalysts depend strongly on the transition metal precursors. The best performing FeCoNi‐derived N‐GT catalyst exhibits excellent ORR and OER activity along with adequate electrochemical durability over a wide potential window (0–1.9 V) in alkaline media. The measured OER current is solely due to desirable O₂ evolution, rather than carbon oxidation. Extensive electrochemical and physical characterization indicated that high graphitization degree, thicker tube walls, proper nitrogen doping, and presence of FeCoNi alloy particles are vital for high bifunctional activity and electrochemical durability of tubular carbon catalysts.     

Nanocarbon Electrocatalysts for Oxygen Reduction in Alkaline Media for Advanced Energy Conversion and Storage

Alkaline oxygen electrocatalysis, targeting anion exchange membrane fuel cells, Zn‐air batteries, and alkaline‐based Li‐air batteries, has become a subject of intensive investigation because of its advantages compared to its acidic counterparts in reaction kinetics and materials stability. However, significant breakthroughs in the design and synthesis of efficient oxygen reduction catalysts from earth‐abundant elements instead of precious metals in alkaline media remain in high demand. Carbon composite materials have been recognized as the most promising because of their reasonable balance between catalytic activity, durability, and cost. In particular, heteroatom (e.g., N, S, B, or P) doping can tune the electronic and geometric properties of carbon, providing more active sites and enhancing the interaction between carbon structure and active sites. Importantly, involvement of transition metals appears to be necessary for achieving high catalytic activity and improved durability by catalyzing carbonization of nitrogen/carbon precursors to form highly graphitized carbon nanostructures with more favorable nitrogen doping. Recently, a synergetic effect was found between the active species in nanocarbon and the loaded oxides/sulfides, resulting in much improved activity. This report focuses on these carbon composite catalysts. Guidance for rational design and synthesis of advanced alkaline ORR catalysts with improved activity and performance durability is also presented.     

In Situ “Chainmail Catalyst” Assembly in Low‐Tortuosity,Hierarchical Carbon Frameworks for Efficient and Stable Hydrogen Generation

The chainmail catalysts (transition metals or metal alloys encapsulated in carbon) are regarded as stable and efficient electrocatalysts for hydrogen generation. However, the fabrication of chainmail catalysts usually involves complex chemical vapor deposition (CVD) or prolonged calcination in a furnace, and the slurry‐based electrode assembly of the chainmail catalysts often suffers from inferior mass transfer and an underutilized active surface. In this work, a freestanding wood‐based open carbon framework is designed embedded with nitrogen (N) doped, few‐graphene‐layer‐encapsulated nickel iron (NiFe) alloy nanoparticles (N‐C‐NiFe). 3D wood‐derived carbon framework with numerous open and low‐tortuosity lumens, which are decorated with carbon nanotubes (CNTs) “villi”, can facilitate electrolyte permeation and hydrogen gas removal. The chainmail catalysts of the N‐C‐NiFe are uniformly in situ assembled on the CNT “villi” using a rapid heat shock treatment. The high heating and quenching rates of the heat shock method lead to formation of the well‐dispersed ultrafine nanoparticles. The self‐supported wood‐based carbon framework decorated with the chainmail catalyst displays high electrocatalytic activity and superior cycling durability for hydrogen evolution. The unique heat shock method offers a promising strategy to rapidly synthesize well‐dispersed binary and polynary metallic nanoparticles in porous matrices for high‐efficiency electrochemical energy storage and conversion.     

Tailoring FeN4 Sites with Edge Enrichment for Boosted Oxygen Reduction Performance in Proton Exchange Membrane Fuel Cell

Transition metal atoms with corresponding nitrogen coordination are widely proposed as catalytic centers for the oxygen reduction reaction (ORR) in metal–nitrogen–carbon (M–N–C) catalysts. Here, an effective strategy that can tailor Fe–N–C catalysts to simultaneously enrich the number of active sites while boosting their intrinsic activity and utilization is reported. This is achieved by edge engineering of FeN₄ sites via a simple ammonium chloride salt‐assisted approach, where a high fraction of FeN₄ sites are preferentially generated and hosted in a graphene‐like porous scaffold. Theoretical calculations reveal that the FeN₄ moieties with adjacent pore defects are likely to be more active than the nondefective configuration. Coupled with the facilitated accessibility of active sites, this prepared catalyst, when applied in a practical H₂–air proton exchange membrane fuel cell, delivers a remarkable peak power density of 0.43 W cm^?2, ranking it as one of the most active M–N–C catalysts reported to date. This work provides a new avenue for boosting ORR activity by edge manipulation of FeN₄ sites.     

Bimetallic Zeolitic Imidazolite Framework Derived Carbon Nanotubes Embedded with Co Nanoparticles for Efficient Bifunctional Oxygen Electrocatalyst

Bifunctional oxygen catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with high activities and low‐cost are of prime importance and challenging in the development of fuel cells and rechargeable metal–air batteries. This study reports a porous carbon nanomaterial loaded with cobalt nanoparticles (Co@NC‐x/y) derived from pyrolysis of a Co/Zn bimetallic zeolitic imidazolite framework, which exhibits incredibly high activity as bifunctional oxygen catalysts. For instance, the optimal catalyst of Co@NC‐3/1 has the interconnected framework structure between porous carbon and embedded carbon nanotubes, which shows the superb ORR activity with onset potential of ≈1.15 V and half‐wave potential of ≈0.93 V. Moreover, it presents high OER activity that can be further enhanced to over commercial RuO₂ by P‐doped with overpotentials of 1.57 V versus reversible hydrogen electrode at 10 mA cm^?2 and long‐term stability for 2000 circles and a Tafel slope of 85 mV dec^?1. Significantly, the nanomaterial demonstrates better catalytic performance and durability than Pt/C for ORR and commercial RuO₂ and IrO₂ for OER. These findings suggest the importance of a synergistic effect of graphitic carbon, nanotubes, exposed Co–N_x active sites, and interconnected framework structure of various carbons for bifunctional oxygen electrocatalysts.     

Metal‐Organic Framework‐Derived Non‐Precious Metal Nanocatalysts for Oxygen Reduction Reaction

By virtue of diverse structures and tunable properties, metal‐organic frameworks (MOFs) have presented extensive applications including gas capture, energy storage, and catalysis. Recently, synthesis of MOFs and their derived nanomaterials provide an opportunity to obtain competent oxygen reduction reaction (ORR) electrocatalysts due to their large surface area, controllable composition and pore structure. This review starts with the introduction of MOFs and current challenges of ORR, followed by the discussion of MOF‐based non‐precious metal nanocatalysts (metal‐free and metal/metal oxide‐based carbonaceous materials) and their application in ORR electrocatalysis. Current issues in MOF‐derived ORR catalysts and some corresponding strategies in terms of composition and morphology to enhance their electrocatalytic performance are highlighted. In the last section, a perspective for future development of MOFs and their derivatives as catalysts for ORR is discussed.     

Controlling the Active Sites of Sulfur‐Doped Carbon Nanotube–Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

Controlling active sites of metal‐free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). Many attempts have been made to develop metal‐free catalysts, but the lack of understanding of active‐sites at the atomic‐level has slowed the design of highly active and stable metal‐free catalysts. A sequential two‐step strategy to dope sulfur into carbon nanotube–graphene nanolobes is developed. This bidoping strategy introduces stable sulfur–carbon active‐sites. Fluorescence emission of the sulfur K‐edge by X‐ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM‐EELS) mapping and spectra confirm that increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm^?2, but also retains 100% of stability after 75 h. The bidoped sulfur carbon nanotube–graphene nanolobes behave like the state‐of‐the‐art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm^?2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light‐weight bidoped sulfur carbon nanotubes are potential candidates for next‐generation metal‐free regenerative fuel cells.     

Post Iron Decoration of Mesoporous Nitrogen‐Doped Carbon Spheres for Efficient Electrochemical Oxygen Reduction

Iron–nitrogen–carbon (Fe–N–C) catalysts are considered as the most promising nonprecious metal catalysts for oxygen reduction reactions (ORRs). Their synthesis generally involves complex pyrolysis reactions at high temperature, making it difficult to optimize their composition, pore structure, and active sites. This study reports a simple synthesis strategy by reacting preformed nitrogen‐doped carbon scaffolds with iron pentacarbonyl, a liquid precursor that can effectively form active sites with the nitrogen sites, enabling more effective control of the catalyst. The resultant catalyst possesses a well‐defined mesoporous structure, a high surface area, and optimized active sites. The catalysts exhibit high ORR activity comparable to that of Pt/C catalyst (40% Pt loading) in alkaline media, with excellent stability and methanol tolerance. The synthetic strategy can be extended to synthesize other metal–N–C catalysts.     

Single‐Atom Catalysts: Emerging Multifunctional Materials in Heterogeneous Catalysis

Supported metal nanoparticles are the most widely investigated heterogeneous catalysts in catalysis community. The size of metal nanostructures is an important parameter in influencing the activity of constructed catalysts. Especially, as coordination unsaturated metal atoms always work as the catalytically active centers, decreasing the particle size of the catalyst can greatly boost the specific activity per metal atom. Single‐atom catalysts (SACs), containing single metal atoms anchored on supports, represent the utmost utilization of metallic catalysts and thus maximize the usage efficiency of metal atom. However, with the decreasing of particle size, the surface free energy increases obviously, and tends to aggregate into clusters or particles. Selection of an appropriate support is necessary to interact with isolated atoms strongly, and thus prevents the movement and aggregation of isolated atoms, creating stable, finely dispersed active sites. Furthermore, with uniform single‐atom dispersion and well‐defined configuration, SACs afford great space for optimizing high selectivity and activity. In this review, a detailed discussion of preparing, characterizing, and catalytically testing within this family is provided, including the theoretical understanding of key aspects of SACs materials. The main advantages of SACs as catalysts and the challenges faced for further improving catalytic performance are also highlighted.     

Hollow Palladium‐Gold Nanochains with Periodic Concave Structures as Superior ORR Electrocatalysts and Highly Efficient SERS Substrates

Unique palladium‐gold hollow nanochains (PdAu HCs) with 1D architecture and an ultrathin Pd‐rich skin exhibit fantastic oxygen reduction reaction (ORR) enhancements due to their high conductivity, structural stability, and maximized atomic utilization. More importantly, such PdAu HCs possess periodic concave structures that boost ORR performance. These structures readily form high‐density high‐index facets, and fewer arc edges. Concave structures can deliver strong strain effects and surface charge accumulation is revealed by off‐axis electron holography. In addition, periodic concave structures can provide strong localized surface–plasmon coupling, which means that PdAu HCs have great potential as efficient surface‐enhanced Raman scattering (SERS) substrates. This study offers a novel and general approach for the design of complex noble metal‐based nanostructures as efficient ORR catalysts and SERS substrates.     

Degradation Mechanism and Enhancing Strategies of Oxygen Reduction Reaction Catalyzed by Carbon-Based Metal Free Catalysts in Acidic Solution

Carbon-based metal free catalysts (CMFCs) are far away from commercial availability mainly attributed to their poor oxygen reduction reaction (ORR) performance in acidic environment with the causes remaining obscure. By investigating the heteroatoms (N, B, P, S, Se, and Te)-doped reduced graphene oxides, the degradation mechanism of acidic ORR performance of CMFCs is found to be correlated with the oxygen-baring defects in the carbon sp² lattice, which exhibit overpotentials as low as 0.44 V but weak trapping capabilities for oxygen molecules. These findings not only revise the previously reported strategy of modeling the active sites in the basal plane of CMFCs but also highlight the connections between those active sites and the triple-coordinated VIA group elements (XC₃). Further calculations demonstrate that the XC₃ dimer can efficiently enhance the acidic ORR performance and the 2D trigonal carbon-chalcogenides C₆X (X = S, Se, and Te) are accordingly designed toward acidic ORR, which contain homogeneously distributed basal plane active sites and exhibit low overpotentials but strong trapping capabilities for oxygen molecules. This work will help to cease the debates on the active sites in CMFCs for ORR in both acidic and alkaline solutions and to open a new avenue to design CMFCs independent on doping strategy.     

Towards Engineering Nanoporous Platinum Thin Films for Highly Efficient Catalytic Applications

Porous metals attract significant interest for use in diverse electrochemical catalytic applications. However the fabrication of scalable and controlled porous metal structures on the nanoscale, particularly with highly catalytic pure Pt, still remains a significant challenge. We demonstrate highly engineered nanoporous Pt thin films by the dealloying of a Pt‐Si binary alloy system with a predetermined alloy composition. Controlled pore dimensions and nanostructures are obtained by tailoring the Pt‐Si alloy composition followed by selective Si etching. As a result, isotropic open nanopores are formed in continuous Pt ligaments and the porosity becomes larger on increasing the Si/Pt atomic ratio, which leads to the formation of a higher surface area and active catalytic sites. The formed nanoporous Pt film shows a 32‐times‐higher catalytic activity than Pt/C catalysts, with a high current density and low charge‐transfer resistance during methanol electro‐oxidation. The results reported here open up possibilities to develop high‐performance and reliable catalytic electrodes in energy and environmental applications.     

Efficiently Enhancing Oxygen Reduction Electrocatalytic Activity of MnO2 Using Facile Hydrogenation

Improving the electrocatalytic oxygen reduction reaction (ORR) activity of transition metal oxides is important for the development of non‐noble metal catalysts that are used in metal‐air batteries and fuel cells. Here, a novel facile strategy of hydrogenation to significantly enhance the ORR performance of MnO₂. The hydrogenated MnO₂ (H‐MnO₂), which is prepared through a simple heat treatment in hydrogen gas, shows characteristics of modified lattice/surface structures and increased electrical conductivity. In 0.1 M KOH aqueous solution, the prepared H‐MnO₂ exhibits high activity toward the oxygen electrocatalysis with more positive onset potential (≈60 mV), ≈14% larger of limiting current, lower yield of peroxide species, and better durability than the pristine oxide. Further conductivity testing and density functional theory (DFT) studies reveal the faster kinetics of ORR after hydrogenation is due to the formation of hydrogen bonds and altered microstructure and improved electronic properties. These results highlight the importance of hydrogenation as a facile yet effective strategy to improve the catalytic activity of transition metal oxides for ORR‐based applications.     

Recent Development of Ni/Fe‐Based Micro/Nanostructures toward Photo/Electrochemical Water Oxidation

The oxygen evolution reaction (OER), as an important process involved in water splitting and rechargeable metal–air batteries, has drawn increasing attention in the context of clean energy generation and efficient energy storage. This review concerns the progress and new discoveries in the field of Ni/Fe‐based micro/nanostructures toward electrochemical and photo‐electrochemical (PEC) water oxidation during last few years. First, toward the design and construction of new electrocatalysis, different types of current Ni/Fe‐based compounds for OER are summarized. The mechanism studies of the active phases and positions of Ni/Fe‐based micro/nanostructures are further introduced to understand the properties of catalytic active sites, which could facilitate further improving the performance of Ni/Fe‐based OER electrocatalysts. Second, splitting water using sunlight with low overpotential is another important target in making solar‐to‐hydrogen micro/nanodevices, and thus attention is then focused on the development of several important Ni/Fe‐based PEC catalysts. Third, the recent theoretical calculations on the OER mechanism during water splitting and insights into electronic structures are analyzed; finally, the future trends and perspectives are also discussed briefly.     

Enhanced Cathodic Oxygen Reduction and Power Production of Microbial Fuel Cell Based on Noble‐Metal‐Free Electrocatalyst Derived from Metal‐Organic Frameworks

Microbial fuel cell (MFC) can generate electricity from organic substances based on anodic electrochemically active microorganisms and cathodic oxygen reduction reaction (ORR), thus exhibiting promising potential for harvesting electric energy from organic wastewater. The ORR performance is crucial to both power production efficiency and overall cost of MFC. A new type of metal‐organic‐framework‐derived electrocatalysts containing cobalt and nitrogen‐doped carbon (CoNC) is developed, which is effective to enhance activity, selectivity, and stability toward four‐electron ORR in pH‐neutral electrolyte. When glucose is used as the substrate, the maximum power density of 1665 mW m^?2 is achieved for the optimized CoNC pyrolyzed at 900 °C, which is 39.8% higher than that of 1191 mW m^?2 for commercial Pt/C catalyst in the single‐chamber MFC. The improved performance of CoNC catalyst can be attributed to large surface area, microporous nature, and the involvement of nitrogen‐coordinated cobalt species. These properties enable the efficient ORR by increasing the active sites and enhancing mass transfer of oxygen and protons at “water‐flooding” three‐phase boundary where ORR occurs. This work provides a proof‐of‐concept demonstration of a noble‐metal‐free high‐efficiency and cost‐effective ORR electrocatalyst for effective recovery of electricity from biomass materials and organic wastewater in MFC.     

Apically Dominant Mechanism for Improving Catalytic Activities of N‐Doped Carbon Nanotube Arrays in Rechargeable Zinc–Air Battery

The oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in zinc–air batteries (ZABs) require highly efficient, cost‐effective, and stable electrocatalysts as alternatives to high cost and low poison resistant platinum group metals (PGM) catalysts. Although nitrogen‐doped carbon nanotube (NCNT) arrays are now capable of catalyzing ORR efficiently, their hydrophobic surface and base‐growth mode are found to limit the catalytic performance in the practical ZABs. Here, the concept of an apically dominant mechanism in improving the catalytic performance of NCNT by precisely encapsulating CoNi nanoparticles (NPs) within the apical domain of NCNT on the Ni foam (denoted as CoNi@NCNT/NF) is demonstrated. The CoNi@NCNT/NF exhibits a more excellent catalytic performance toward both ORR and OER than that of traditional NCNT derived from the base‐growth method. The ZAB coin cell using CoNi@NCNT/NF as an air electrode shows a peak power density of 127 mW cm^?2 with an energy density of 845 Wh kg_Zn^?1 and rechargeability over 90 h, which outperforms the performance of PGM catalysts. Density functional theory calculations reveal that the ORR catalytic performance of the CoNi@NCNT/NF is mainly attributed to the synergetic contributions from NCNT and the apical active sites on NCNT near to CoNi NPs.     

Electronic and Defective Engineering of Electrospun CaMnO3 Nanotubes for Enhanced Oxygen Electrocatalysis in Rechargeable Zinc–Air Batteries

Rational design and massive production of bifunctional catalysts with superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are essential for developing metal–air batteries and fuel cells. Herein, controllable large‐scale synthesis of sulfur‐doped CaMnO₃ nanotubes is demonstrated via an electrospinning technique followed by calcination and sulfurization treatment. The sulfur doping can not only replace oxygen atoms to increase intrinsic electrical conductivity but also introduce abundant oxygen vacancies to provide enough catalytically active sites, which is further demonstrated by density functional theory calculation. The resulting sulfur‐modified CaMnO₃ (CMO/S) exhibits better electrocatalytic activity for ORR and OER in alkaline solution with higher stability performance than the pristine CMO. These results highlight the importance of sulfur treatment as a facile yet effective strategy to improve the ORR and OER catalytic activity of the pristine CaMnO₃. As a proof‐of‐concept, a rechargeable Zn–air battery using the bifunctional catalyst exhibits a small charge–discharge voltage polarization, and long cycling life. Furthermore, a solid‐state flexible and rechargeable Zn–air battery gives superior discharge–charge performance and remarkable stability. Therefore, the CMO/S nanotubes might be a promising replacement to the Pt‐based electrocatalysts for metal–air batteries and fuel cells.     

Definitive Structural Identification toward Molecule‐Type Sites within 1D and 2D Carbon‐Based Catalysts

Developing facile preparation routes and atomic‐level characterization methods for single‐atom catalysts is highly desirable but still challenging. Herein, a general strategy is proposed to construct transition metal single atoms within 1D and 2D carbon supports. The carbon supports, typically graphene and carbon nanotubes, are coated with various transition metal‐containing bimetal hydroxides, followed by polydopamine coating and high‐temperature pyrolysis. X‐ray absorption fine structure spectroscopy measurements and simulations efficiently indicate that single atoms (Co, Fe, or Cu) are captured within the applied carbon supports, distinctively forming exclusive molecule‐type sites. As a proof‐of‐concept application, the obtained catalysts exhibit remarkable performance for electrochemical oxygen reduction reaction, even surpassing commercial Pt/C catalyst. The developed versatile route opens up new avenues for the design of carbon‐based catalysts with definite molecular active sites. The atomic‐level structural identifications provide significant guidance for mechanistic studies toward single‐atom catalysts.