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Atomically dispersed iron–nitrogen–carbon catalysts are promised, low‐cost, and high‐performance electrocatalysts for the Oxygen Reduction Reaction (ORR) in fuel cells. However, most Fe–N–C materials are produced via pyrolysis at a high temperature and it is difficult to characterise the precise Fe–N configurations. This can lead to confusion surrounding the best chemical and coordination environment for Fe and understanding the subsequent ORR mechanisms. In this work, Fe porphyrin is used to produce a specific Fe–N environment, therefore allowing the role and activity of this environment to be studied. Carbon nanotubes (CNTs) are covalently functionalized with iron 5,10,15,20‐triphenylporphyrin (FeTPP) motifs via aryl diazonium methodology, enabling the exact role of only the Fe‐Pyrrolic N4 configuration of FeTPP in ORR to be studied and better understood. Upon covalent functionalization, a high electrochemical active site density of 1.12 × 1015 sites cm−2, approximately six‐fold more than that of noncovalently functionalized samples with 12.7% electrochemical active site. The heightened active site density and superior electrochemical active site utilization (12.7%) lead to the more favorable 4‐electron pathway for the ORR. Furthermore, a preliminary discussion regarding the selectivity of the ORR pathway is initiated. [ABSTRACT FROM AUTHOR]

The electrochemical CO2 reduction reaction (CO2RR) to value‐added chemicals with renewable electricity is a promising method to decarbonize parts of the chemical industry. Recently, single metal atoms in nitrogen‐doped carbon (MNC) have emerged as potential electrocatalysts for CO2RR to CO with high activity and faradaic efficiency, although the reaction limitation for CO2RR to CO is unclear. To understand the comparison of intrinsic activity of different MNCs, two catalysts are synthesized through a decoupled two‐step synthesis approach of high temperature pyrolysis and low temperature metalation (Fe or Ni). The highly meso‐porous structure results in the highest reported electrochemical active site utilization based on in situ nitrite stripping; up to 59±6% for NiNC. Ex situ X‐ray absorption spectroscopy (XAS) confirms the penta‐coordinated nature of the active sites. The catalysts are amongst the most active in the literature for CO2 reduction to CO. The density functional theory calculations (DFT) show that their binding to the reaction intermediates approximates to that of Au surfaces. However, it is found that the turnover frequencies (TOFs) of the most active catalysts for CO evolution converge, suggesting a fundamental ceiling to the catalytic rates. [ABSTRACT FROM AUTHOR]

Atomically dispersed transition metal‐nitrogen‐carbon catalysts are emerging as low‐cost electrocatalysts for the oxygen reduction reaction in fuel cells. However, a cost‐effective and scalable synthesis strategy for these catalysts is still required, as well as a greater understanding of their mechanisms. Herein, iron, nitrogen co‐doped carbon spheres (Fe@NCS) have been prepared via hydrothermal carbonization and high‐temperature post carbonization. It is determined that FeN4 is the main form of iron existing in the obtained Fe@NCS. Two different precursors containing Fe2+ and Fe3+ are compared. Both chemical and structural differences have been observed in catalysts starting from Fe2+ and Fe3+ precursors. Fe2+@NCS‐A (starting with Fe2+ precursor) shows better catalytic activity for the oxygen reduction reaction. This catalyst is studied in an anion exchange membrane fuel cell. The high open‐circuit voltage demonstrates the potential approach for developing high‐performance, low‐cost fuel cell catalysts. [ABSTRACT FROM AUTHOR]

Sustainable energy production at an acceptable cost is key for its widespread application. At present, noble metals and metal oxides are the most widely used for electrocatalysis, but they suffer from low selectivity, poor durability, and scarcity. Because of this, metal‐free carbons have become the subject of great interest as promising alternative electrocatalysts for energy conversion and storage devices, and remarkable progress has been accomplished in the advance of metal‐free carbons as electrocatalysts for renewable energy technologies. Particularly interesting are 3D porous carbon architectures, which exhibit outstanding features for electrocatalysis applications, including broad range of active sites, interconnected porosity, high conductivity, and mechanical stability. This review summarizes the latest advances in 3D porous carbon structures for oxygen and hydrogen electrocatalysis. The structure–performance relationship of these materials is consequently rationalized and perspectives on creating more efficient 3D carbon electrocatalysts are suggested. [ABSTRACT FROM AUTHOR]

High activity, selectivity and recyclability are crucial parameters in the design of performant catalysts. Furthermore, depletion of platinum‐group metals (PGM) drives further research towards highly available metal‐based catalysts. In this framework, iron‐based active sites supported on nitrogen‐doped carbon materials (Fe/N@C) have been explored to tackle important applications in organic chemistry, for both oxidation and reduction of C−O/C−N bonds, as well as in electrocatalysis for energy applications. This versatile reactivity makes them ideal substitutes to PGM‐based catalysts, being based on abundant elements. Despite important advances in material science and characterisation techniques allowing the analysis of heterogeneous/electro‐ catalysts at the atomic scale, the nature of the catalytically active sites in Fe/N@C remains elusive. Most recent theoretical studies point at individual FeNx single sites as the origin of the catalytic activity. Although their identification is still challenging with current technology, establishing their real nature will foster further research on these PGM‐free and redox‐polyvalent catalysts. In this review, we provide an overview of their applications in both thermal and electrochemical processes. Throughout the review, we highlight the different characterisation techniques employed to gain insight into the catalyst's active sites. [ABSTRACT FROM AUTHOR]

A hard templating method, using SBA‐15 in combination with glucose solution and different heteroatom precursors, has been employed to investigate the influence of the different heteroatom dopants nitrogen, boron, sulfur, and phosphorus on carbon electrocatalysts for the oxygen reduction reaction. Samples were synthesized under the same conditions and resulted in a similar morphology and surface areas around 1000 m2/g. Incorporating nitrogen into the carbon matrix was found to be easier than for boron or phosphorus, while sulfur doping proved problematic and only yielded 2 at% of sulfur or less. Different dopant concentrations as well as a combination of dopants suggested that nitrogen was the only heteroatom exerting an actual influence on the catalytic activity, resulting in higher electron transfer numbers. The other dopants exhibited a similar performance regardless of the dopant content, though slightly improved when compared to an undoped control sample. These findings indicate that incorporated nitrogen can act as catalytic sites, while boron, sulfur and phosphorus can enhance the catalytic activity by possibly creating defects in the carbon matrix. [ABSTRACT FROM AUTHOR]

The aqueous oxygen reduction reaction (ORR) has recently received increased attention due to its critical role in clean and sustainable energy‐generation technologies, such as proton exchange membranes (PEM) fuel cells, alkaline fuel cells and Zn–air batteries. The sluggish kinetics associated with ORR result from multistep electron‐transfer process. The slow kinetics are partially related to the O2 adsorption process onto the catalyst, which happens at the triple‐phase boundary (TPB) of the electrocatalyst–electrolyte–oxygen interface. Hence, tremendous efforts have been devoted to improving the intrinsic properties of electrocatalysts such as active sites, electrical conductivity and porosity. Engineering the electrocatalyst's interfacial properties is another critical issue in ORR, however less described in the literature. The surface of the catalyst provides the microenvironment for the triple boundary interface reaction, which directly influences its electrocatalytic activity and the kinetics. This Minireview is a summary of the existing literature on manipulating the interfacial surface of non‐precious metal catalysts at the triple point between the solid catalyst, the aqueous electrolyte and the O2 gas with the aim of improving the ORR efficiency. Various approaches towards improving the wettability and nanostructuring the catalyst surface to boost the activity of the surface‐active sites and provide improved stability are discussed. Promoting adsorption: The sluggish kinetics resulting from multistep electron transfer processes is the main concern in ORR. Promoting O2 adsorption, which happens on the triple‐phase boundary (TPB) of electrocatalyst–electrolyte–oxygen interface can overcome the slow kinetics. In this paper we review some of the existing surface engineering strategies in the literature aiming to manipulate the triple point boundary (TPB) to promote the aqueous ORR. [ABSTRACT FROM AUTHOR]

Abstract: Carbon and transition metals have emerged as promising candidates for many energy storage and conversion devices. They facilitate charge transfer reactions whilst showing a good stability. These materials, fabricated as freestanding electrodes pose the potential of simplified electrode manufacturing procedures whilst demonstrating excellent electrocatalytic, mechanical, and structural properties, resulting from interconnected (via chemical or van der Waals force bonded) network structures. In such freestanding configuration, the lack of a binder leads to a better conductivity, ease in the manufacturing processing, and allows a lower catalyst mass loading, all of which lead to obvious benefits. This Minireview summarizes different fabrication techniques of freestanding non‐precious‐metal oxygen electrocatalysts along with their performance towards the oxygen evolution reaction (OER) and/or oxygen reduction reaction (ORR). Here, we discuss electrocatalysts produced by using freestanding substrates and those obtained through the self‐assembly of different precursors. The advantages of using freestanding versus non‐freestanding configurations are also pondered. Challenges and perspectives for freestanding electrocatalysts are presented at the end of the Minireview as a guideline for future studies in the field. This work is expected to serve as inspiration for science colleagues to develop further studies into design, processing and testing strategies of freestanding low‐cost oxygen electrocatalysts. [ABSTRACT FROM AUTHOR]

Abstract: An effective strategy is proposed to enhance the oxygen reduction reaction (ORR) performance of multiwall carbon nanotubes (MWCNTs) in both acid and alkaline electrolytes by coating them with a layer of biomass derivative N‐doped hydrothermal carbons. The N‐doped amorphous carbon coating plays triple roles: it (i) promotes the assembly of MWCNTs into a 3D network therefore improving the mass transfer and thus increasing the catalytic activity; (ii) protects the Fe‐containing active sites, present on the surface of the MWCNTs, from H2O2 poisoning; (iii) creates nitrogenated active sites and hence further enhances ORR activity and robustness. [ABSTRACT FROM AUTHOR]

A one-pot, hydrothermal synthesis of nitrogen and sulfur dual doped carbon aerogels is presented, derived from our previously published hydrothermal carbonization approach. Two co-monomers, S-(2-thienyl)-l-cysteine (TC) and 2-thienyl carboxaldehyde (TCA), were used for sulfur incorporation, giving rise to distinct morphologies and varying doping levels of sulfur. Nitrogen-doping levels of 5 wt% and sulfur-doping levels of 1 wt% (using TCA) to 4 wt% (using TC) were obtained. A secondary pyrolysis step was used to further tune the carbon aerogel conductivity and heteroatom binding states. By comparing solely nitrogen-doped with nitrogen- and sulfur-doped carbon aerogels, it was observed that the presence of sulfur improves the overall electrocatalytic activity of the carbon material in both basic and acidic media. This study of the synergistic effect of combined sulfur- and nitrogen-doping in the catalysis of the “oxygen reduction reaction” (ORR) is expected to be significant to future research concerning the improvement of heterogeneous, metal-free, carbon-based catalysts. [ABSTRACT FROM AUTHOR]

The hydrothermal synthesis of nitrogen-doped monolithic carbon aerogels derived from sustainable precursors (i.e.d-glucose and ovalbumin) is presented. The protein acts as nitrogen donor and surface stabilizing agent in this saccharide hydrothermal carbonization, to generate high surface area aerogels (＞240 m2g−1) composed of functional continuous large diameter mesopores with excellent hierarchical transport architecture. Post-carbonization treatment controls surface chemistry (e.g. C or N condensation), facilitating tuneable physicochemical properties on a unique continuous 3D carbonaceous pore structure. This highly flexible synthesis lays the basis for the development of a new generation of sustainable (heteroatom-doped) porous carbon aerogels suitable for a range of high value applications. [ABSTRACT FROM AUTHOR]

Electrocatalysis: 3D Carbon Materials for Efficient Oxygen and Hydrogen Electrocatalysis (Adv. Keywords: 3D porous carbons; electrocatalysis; hydrogen evolution; oxygen evolution; oxygen reduction 3D porous carbons, electrocatalysis, hydrogen evolution, oxygen evolution, oxygen reduction. [Extracted from the article]

Commercial polymer electrolyte membrane fuel cells have relied on scares Platinum to catalyse the kinetically sluggish oxygen reduction reaction occurring at their anodes. Over the last decade organic materials, frequently based on graphitic structures have been demonstrated as promising alternative electrocatalysts to the noble metals. Researchers typically utilize ultrasonic treatment as part of the synthesis procedure to achieve homogeneous dispersion of graphitic carbon prior to. Herein we investigate the implications of the structural and compositional changes induced by the ultrasonication treatment on boron-doped reduced graphene oxide for oxygen reduction reaction. It is shown that ultrasonication pre-treatment prior to the boron doping and reduction of graphene oxide via hydrothermal process step leads to the increase of both substitutional B and electrocatalytic surface area, with associated reduction of average pore size diameter, leading to a significant improvement in the oxygen reduction reaction performance, with respect to the non-ultrasonicated material. It is proposed that the higher degree of substitutional doping of boron is a result of formation of the additional epoxy functionalities on graphitic planes, which act as a doping site for boric acid. • Ultrasonication enables higher doping of boron into Graphene oxide. • Longer ultrasonication times leads to higher substitutional boron. • Longer ultrasonication times leads to higher ORR activity. [ABSTRACT FROM AUTHOR]

Pyridinic-N configurations and intrinsic defects on nanocarbons have been regarded as potentially active-sites for the oxygen reduction reaction (ORR). In this work, a facile strategy is demonstrated to achieve pyridinic-N dominated porous carbon nanosheets with edge-enriched defective nature through the selection of the bio-precursor guanine as C/N sources. It is able to achieve high contents of pyridinic-N dominated (48.1% from gross N) species and the few-layers carbon architectures with hierarchical porosity by a template-free carbonization method. These 2D carbon structures are of low cost, scalable and economically attractive while based on renewable and highly abundant resources. As a result, the optimized catalyst delivers a significantly enhanced electrocatalytic performance for ORR under wide range of pH from alkaline to acid, i. e. possessing a 30 mV more positive half-wave potential (0.885 V) than Pt/C (0.855 V) catalyst in 0.1 M KOH, and very close activities to Pt/C in 0.1 M PBS and 0.1 M HClO 4 solution. This ORR performance is attributed to the synergistic effects of unique graphene-like architecture, high porosity, and coexistences of high contents of pyridinic-N species and abundant edge/defect sites. Image 1 A facile strategy is demonstrated to achieve pyridinic-N dominated porous carbon nanosheets with edge-enriched defective nature through the selection of the biological nucleobase precursor as C/N sources. [ABSTRACT FROM AUTHOR]

Implementing metal-free electrocatalysts for the oxygen reduction reaction (ORR) and revealing crucial chemical or topographical parameters driving their activity are vital for the development of power cells. The carbon-based catalysts are very often synthesized through carbonization of biopolymers, in particular, those one containing nitrogen groups such as chitosan. Unfortunately, the resulting carbonaceous materials usually lack specific porosity and exhibit low catalytic activity. Here, we demonstrate that pyrolysis of chitosan in a ZnCl 2 melt assisted by the presence of LiCl results not only in a highly porous activated carbon material with a specific surface area of 1317.97 m 2 /g and the total nitrogen content of 6.5%, but also induces unexpected curvature in the grown graphitic layers. This is the first work that shows curved graphene layers obtained from a biopolymer precursor by its pyrolytic decomposition in the melted salt media. On the other hand, a carbonaceous material obtained from chitosan but without the salts has very low specific surface area of 7.8 m 2 /g, possesses no specific structural features, and contains 4.7% of nitrogen. The electrochemical studies show, that the former material is highly active towards four-electron pathway of the ORR in terms of an onset potential (0.89 V vs RHE) and the turnover frequency (TOF max  = 0.095 e site −1  s −1 ). We attribute this high catalytic performance to the presence of the pyridinic and pyrrolic sites in the structure. The ORR kinetics is probably further promoted by curvature in the graphitic layers. [ABSTRACT FROM AUTHOR]

Developing the low-cost, highly active carbonaceous materials for oxygen reduction reaction (ORR) catalysts has been a high-priority research direction for durable fuel cells. In this paper, two novel N-doped carbonaceous materials with flaky and rod-like morphology using the natural halloysite as template are obtained from urea nitrogen source as well as glucose (denoted as GU) and furfural (denoted as FU) carbon precursors, respectively, which can be directly applied as metal-free electrocatalysts for ORR in alkaline electrolyte. Importantly, compared with a benchmark Pt/C (20wt%) catalyst, the as-prepared carbon catalysts demonstrate higher retention in diffusion limiting current density (after 3000 cycles) and enhanced methanol tolerances with only 50-60mV negative shift in half-wave potentials. In addition, electrocatalytic activity, durability and methanol tolerant capability of the two N-doped carbon catalysts are systematically evaluated, and the underneath reasons of the outperformance of rod-like catalysts over the flaky are revealed. At last, the produced carbonaceous catalysts are also used as cathodes in the single cell H 2 /O 2 anion exchange membrane fuel cell (AEMFC), in which the rod-like FU delivers a peak power density as high as 703 mW cm −2 ( vs. 1106 mW cm −2 with a Pt/C benchmark cathode catalyst). [ABSTRACT FROM AUTHOR]

A simple, cost-effective and scalable approach for the synthesis of N-doped mesoporous carbons that are effective as ORR catalysts is reported. The synthesis procedure involves two steps: a) production of mesoporous carbons using a template-free approach based on the carbonization of citrate salts of zinc and calcium, and b) N-doping by heat treatment in the presence of melamine. The resulting N-doped carbon possess a high specific surface area, a porosity made up exclusively of mesopores and a large amount of nitrogen functionalities (∼8–9 wt%). When used as an electrocatalyst for the oxygen reduction reaction (ORR), the metal-free carbon materials predominantly catalyze the 4 e − process, with an onset potential of 0.9 V ( vs. RHE) and a superior kinetic current density (∼17 mA cm −2 ) to that of Pt/C at ∼0.6 V under basic conditions. In addition, the developed catalysts show a higher stability than commercial Pt/C and excellent electrocatalytic selectivity against methanol crossover. [ABSTRACT FROM AUTHOR]

To resolve an increasing global demand in energy, a source of sustainable and environmentally friendly energy is needed. Microbial fuel cells (MFC) hold great potential as a sustainable and green bioenergy conversion technology that uses waste as the feedstock. This work pursues the development of an effective small-scale MFC for energy generation from urine. An innovative air-cathode miniature MFC was developed, and the effect of electrode length was investigated. Two different biomass derived catalysts were also studied. Doubling the electrode length resulted in the power density increasing by one order of magnitude (from 0.053 to 0.580 W m −3 ). When three devices were electrically connected in parallel, the power output was over 10 times higher compared to individual units. The use of biomass-derived oxygen reduction reaction catalysts at the cathode increased the power density generated by the MFC up to 1.95 W m −3 , thus demonstrating the value of sustainable catalysts for cathodic reactions in MFCs. [ABSTRACT FROM AUTHOR]

Herein we presented, for the first time, facile fabrication of nitrogen doped (0.5–4 wt.%) porous carbon aerogels using biomass derivatives ( i.e. glucose or cellulose) as the carbon precursor and soy protein as both the nitrogen precursor and the structure directing agent. Through post thermal treatment to improve the electrical conductivity and porosity, the obtained materials showed excellent oxygen reduction reaction (ORR) catalytic activity. The electrochemical performance was further enhanced after platinum impregnation, combining the advantages of small over-potential from platinum catalyst and high limiting current density from the carbon substrate. Therefore, we demonstrated here not only a novel and low cost hydrothermal synthesis route to achieve high-performing metal-free ORR catalyst or carbon substrate for additional metal catalyst, but also a general principle on how to develop metal nanoparticles/carbon hybrids for ORR. [ABSTRACT FROM AUTHOR]