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The development of efficient non-precious metal electrocatalysts for oxygen reduction reaction (ORR) to replace Pt-based methods is crucial for the applications of fuel cells and metal–air batteries. In this study, a bimetallic M-N-C catalyst with highly dispersed dual-atom Fe/Mn-Nx sites immobilized on N-doped bamboo-like carbon nanotubes is prepared by the ball-milling and calcination of dual-MOFs as precursors. The rich N-doping and abundant M–Nx species contribute to the excellent intrinsic ORR activity of the catalyst, and the unique bamboo-like nanotubes morphology is beneficial for facilitating electron transfer and mass transport while simultaneously enabling the exposure of active sites. As expected, the optimized Z-Fe1Mn1-NC catalyst exhibits efficient ORR activity with a half-wave potential (E1/2) of 0.80 V in acid and 0.82 V in alkaline, and a higher electrochemical stability with the current density maintained at 91% (in 0.1 M KOH) and 86% (0.1 M HClO4) of its initial current density after 15 h of a chronoamperometric test at a high potential of 0.7 V. When further applied to Zn–air batteries, the catalyst also delivers a high open-circuit voltage, large power density, and outstanding rate performance. This work provides a novel means of designing dual metal M–Nx site-based M-N-C catalysts for ORR sustainable energy applications. [ABSTRACT FROM AUTHOR]

As energy demand increases, new energy conversion methods are also sought. In this study, two MnO2 and multiwalled carbon nanotube (MWCNT) composites were prepared and decorated with silver using magnetron sputtering, to evaluate their electrocatalytic activity towards the oxygen reduction reaction (ORR). Three nominal thicknesses of Ag layers were used, 5, 10 and 20 nm. The physicochemical characterisation was carried out using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, as well as X-ray photoelectron spectroscopy. The substrate materials (MnO2-MWCNT) were also investigated by X-ray diffraction analysis. The electrochemical studies of the ORR revealed that the activity and stability of the composite catalysts depend on the substrate material and the Ag layer thickness. [ABSTRACT FROM AUTHOR]

Single-atom catalysts are a family of heterogeneous electrocatalysts widely used in energy storage and conversion. The determination of the local structure of the active metal sites is challenging, which limits the establishment of the reliable structure-property relationship of single-atom catalysts. A carbon black-conjugated complex can be used as the model catalyst to probe the intrinsic activity of metal sites with certain local structures. In this work, we prepared carbon black-conjugated [Co(phenanthroline)Cl2], [Co(o-phenylenediamine)Cl2] and [Co(salophen)]. In these catalysts, the Co complexes with well-defined structures are anchored on the edge of carbon black by pyrazine moieties. The number of electrochemical accessible Co sites can be measured from the area of the redox peaks of pyrazine linkers in the cyclic voltammetry curve. Then, the intrinsic electrocatalytic activity of one Co site can be obtained. The catalytic performances of the three catalysts towards oxygen reduction reaction in alkaline conditions were measured. Carbon black-conjugated [Co(salophen)] showed the highest intrinsic activity with the turnover frequency of 0.72 s−1 at 0.75 V vs. the reversible hydrogen electrode. The strategy developed in this work can be used to explore and verify the possible local structure of active sites proposed for single-atom catalysts. [ABSTRACT FROM AUTHOR]

Fe-N-doped carbon (Fe-N-C)-based electrocatalysts are considered to be promising alternatives to replace Pt-based catalysts for oxygen reduction reactions (ORR). Here, we reported a simple and effective approach to prepare Fe-N-C-based electrocatalysts with the shape of two-dimensional nanosheets (termed Fe/NCNSs) to enhance the ORR performance. Fe/NCNSs were prepared by the calcination of Fe/Zn dual-metal ZIFs nanosheets as precursors. Benefiting from its higher specific surface area, electrochemically active surface area, and proportion of pyridinic N and Fe-N, the optimized Fe/NCNS showed excellent ORR performance both in acidic (E1/2 = 0.725 V vs. RHE) and alkaline (E1/2 = 0.865 vs. RHE) media, being 23 mV more negative and 24 mV more positive than that of a commercial Pt/C. The optimized Fe/NCNS also exhibited long durability. In addition, the Zn-air battery with Fe/NCNS-1 and RuO2 as the air catalyst exhibited high power density (1590 mW cm−2 at a current density of 2250 mA cm−2) and superior charging/discharging durability. [ABSTRACT FROM AUTHOR]

Low-cost and highly efficient electrocatalysts for oxygen reactions are highly important for oxygen-related energy storage/conversion devices (e.g., solar fuels, fuel cells, and rechargeable metal-air batteries). In this work, a range of compositionally-tuned cerium-doped CoMn2O4 (Ce-CMO-X) spinels were prepared via oxidizing precipitation and subsequent crystallization method and evaluated as electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The Ce modification into the CMO spinels lead to the changes of surface electronic structure. And Ce-CMO-X catalysts display better electrochemical performance than that of pristine CMO spinel. Among them, Ce-CMO-18% shows the best activity. The Ce-CMO-18% processes a higher ratio of Co3+/Co2+, Mn4+/Mn3+, which is beneficial to ORR performance, while the higher content of oxygen vacancies in Ce-CMO-18% make for better OER performance. Thus, the Ce-doped CMO spinels are potential candidates as bifunctional electrocatalysts for both ORR and OER in alkaline environments. Then, the hybrid Ce-CMO-18%/MWCNTs catalyst was also synthesized, which shows further enhanced ORR and OER activities. It displays an ORR onset potential of 0.93 V and potential of 0.84 V at density of 3 mA cm−2 (at 1600 rpm), which is comparable to commercial Pt/C. The OER onset potential and potential at a current density 10 mA cm-2 are 183 mV and 341 mV. The superior electrical conductivity and oxygen functional groups at the surface of MWCNTs can facilitate the interaction between metal oxides and carbon, which promoted the OER and ORR performances significantly. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) is paid much more attention because of the high overpotential required for driving the four-electron process in the field of storage and sustainable energy conversion, including fuel cell applications. In this paper, PtCo nanoparticles encapsulated on carbon supports were prepared by a simple modified polyol method with ethylene glycol. Structural as well as electrochemical characterizations illustrated that the PtCo/C electrocatalysts had a minimum particle size of 4.8 nm, which is close to the commercial 40 wt% Pt/JM. Moreover, the electrochemical measurements indicated that ORR activity was competitive with the commercial 40 wt% Pt/JM catalyst. The synthesis method is a critical way to produce PtCo/C catalysts for use in polymer electrolyte membranes in fuel cells (PEMFCs). [ABSTRACT FROM AUTHOR]

Proton exchange membrane (PEM) fuel cells using Pt-based materials as electrocatalysts have achieved a decent performance, represented by the launched Toyota Mirai vehicle. The ideal PEM fuel cells consume stored pure hydrogen and air. However, SO2, as a primary air contaminant, may be fed along with air at the cathode, leading to Pt site deactivation. Therefore, it is important to improve the SO2 tolerance of catalysts for the stability of the oxygen reduction reaction (ORR). In this work, we develop the Pt/C-TiO2 catalyst against SO2 poisoning during ORR. Impressively, the hybrid Pt/C-TiO2 catalyst with 20 mass % TiO2 shows the best ORR and anti-toxic performance: the kinetic current density of ORR is 20.5% higher and the degradation rate after poisoning is 50% lower than Pt/C. The interaction between Pt and TiO2 as well as the abundant hydroxyl groups on the surface of TiO2 are both revealed to account for the accelerated removal of poisonous SO2 on Pt surfaces. [ABSTRACT FROM AUTHOR]

The development of non-precious metal electrocatalysts towards oxygen reduction reaction (ORR) is crucial for the commercialisation of polymer electrolyte fuel cells. In this work, cobalt-containing nitrogen-doped porous carbon materials were prepared by a pyrolysis of mixtures of saccharides, cobalt nitrate and dicyandiamide, which acts as a precursor for reactive carbon nitride template and a nitrogen source. The rotating disk electrode (RDE) experiments in 0.1 M KOH solution showed that the glucose-derived material with optimised cobalt content had excellent ORR activity, which was comparable to that of 20 wt% Pt/C catalyst. In addition, the catalyst exhibited high tolerance to methanol, good stability in short-time potential cycling test and low peroxide yield. The materials derived from xylan, xylose and cyclodextrin displayed similar activities, indicating that various saccharides can be used as inexpensive and sustainable precursors to synthesise active catalyst materials for anion exchange membrane fuel cells. [ABSTRACT FROM AUTHOR]

Hollow Pt-based nanoparticles are known to possess the properties of high electrocatalytic activity and durability. Nonetheless, their practical applications as catalytic materials are limited because of the requirement for exhaustive preparation. In this study, we prepared carbon-supported hollow PtNix (x = the moles of the Ni precursor to the Pt precursor in the catalyst preparation step) catalysts using a one-step preparation method, which substantially reduced the complexity of the conventional method for preparing hollow Pt-based catalysts. In particular, this hollow structure formation mechanism was proposed based on extensive characterizations. The prepared catalysts were examined to determine if they could be used as electrocatalysts for the oxygen reduction reaction (ORR). Among the investigated catalysts, the acid-treated hollow PtNi3/C catalyst demonstrated the best ORR activity, which was 3 times higher and 2.3 times higher than those of the commercial Pt/C and acid-treated particulate PtNi3/C catalysts, respectively. [ABSTRACT FROM AUTHOR]

To evaluate supports' effects on catalytic activity toward the oxygen reduction reaction (ORR), a simple and controlled chemical synthesis, involving the hot injection of metal precursors, was developed to produce bimetallic PtNi nanoparticles (75 wt.% Pt and 25 wt.% Ni), supported on carbon nanotubes (CNTs) and carbon nanofibers (CNFs). The synthesized electrocatalyst was characterized using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), and scanning transmission electron microscopy (STEM). To determine the catalytic activity, an electrochemical evaluation of the synthesized catalysts in an acidic medium was performed using cyclic voltammetry (CV), CO stripping, and rotating disk electrode (RDE) tests. The presence of Pt and Ni in the nanoparticles was confirmed by EDS and XRD. Based on the STEM micrographs, the average particle size was 30 nm. Compared to the commercial Pt/C catalyst, the PtNi/CNT catalyst exhibited higher specific activity and slightly lower mass activity toward ORR in a 0.1 M HClO4 electrolyte solution. [ABSTRACT FROM AUTHOR]

The smart choice of polyoxometalates (POMs) and the design of POM@carbon-based composites are promising tools for producing active electrocatalysts for both the oxygen reduction (ORR) and the oxygen evolution reactions (OER). Hence, herein, we report the preparation, characterization and application of three composites based on doped, multi-walled carbon nanotubes (MWCNT_N6) and three different POMs (Na12[(FeOH2)2Fe2(As2W15O56)2]·54H2O, Na12[(NiOH2)2Ni2(As2W15O56)2]·54H2O and Na14[(FeOH2)2Ni2(As2W15O56)2]·55H2O) as ORR and OER electrocatalysts in alkaline medium (pH = 13). Overall, the three POM@MWCNT_N6 composites showed good ORR performance with onset potentials between 0.80 and 0.81 V vs. RHE and diffusion-limiting current densities ranging from −3.19 to −3.66 mA cm−2. Fe4@MWCNT_N6 and Fe2Ni2@MWCNT_N6 also showed good stability after 12 h (84% and 80% of initial current). The number of electrons transferred per O2 molecule was close to three, suggesting a mixed regime. Moreover, the Fe2Ni2@MWCNT_N6 presented remarkable OER performance with an overpotential of 0.36 V vs. RHE (for j = 10 mA cm−2), a jmax close to 135 mA cm−2 and fast kinetics with a Tafel slope of 45 mV dec−1. More importantly, this electrocatalyst outperformed not only most POM@carbon-based composites reported so far but also the state-of-the-art RuO2 electrocatalyst. Thus, this work represents a step forward towards bifunctional electrocatalysts using less expensive materials. [ABSTRACT FROM AUTHOR]

Herein, a promising method to prepare efficient N-doped porous carbon-supported Fe2O3 nanoparticles (Fe2O3/N-PCs) ORR electrocatalysts is presented. The porous carbon was derived from a biomass i.e., mulberry leaf through a cost-effective approach. The existence of diverse compounds containing carbon, oxygen, nitrogen and sulfur in mulberry leaf benefit the formation and uniform dispersion of Fe2O3 nanoparticles (NPs) in the porous carbon. In evaluating the effects of the carbon support on the Fe2O3 NPs towards the ORR, we found that the sample of Fe2O3/N-PCs-850 (Fe2O3/N-PCs obtained at 850 °C) with high surface area of 313.8 m2·g-1 exhibits remarkably superior ORR activity than that of materials acquired under other temperatures. To be specific, the onset potential and reduction peak potential of Fe2O3/N-PCs-850 towards ORR are 0.936 V and 0.776 V (vs. RHE), respectively. The calculated number of electron transfer n for the ORR is 3.9, demonstrating a near four-electron-transfer process. Furthermore, it demonstrates excellent longtime stability and resistance to methanol deactivation compared with Pt/C catalyst. This study provides a novel design of highly active ORR electrocatalysts from low-cost abundant plant products. [ABSTRACT FROM AUTHOR]

Development of inexpensive and robust electrocatalysts towards oxygen reduction reaction (ORR) is crucial for the cost-affordable manufacturing of metal-air batteries and fuel cells. Here we show that cross-linked CoMoO4 nanosheets and reduced graphene oxide (CoMoO4/rGO) can be integrated in a hybrid material under one-pot hydrothermal conditions, yielding a composite material with promising catalytic activity for oxygen reduction reaction (ORR). Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were used to investigate the efficiency of the fabricated CoMoO4/rGO catalyst towards ORR in alkaline conditions. The CoMoO4/rGO composite revealed the main reduction peak and onset potential centered at 0.78 and 0.89 V (vs. RHE), respectively. This study shows that the CoMoO4/rGO composite is a highly promising catalyst for the ORR under alkaline conditions, and potential noble metal replacement cathode in fuel cells and metal-air batteries. [ABSTRACT FROM AUTHOR]

In the current work, heteroatom-doped graphene materials containing different atomic ratios of nitrogen and sulphur were employed as electrocatalysts for the oxygen reduction reaction (ORR) in acidic and alkaline media. To this end, the hydrothermal route and different chemical reducing agents were employed to synthesize the catalytic materials. The physicochemical characterization of the catalysts was performed by several techniques, such as X-ray diffraction, Raman spectroscopy and elemental analysis; meanwhile, the electrochemical performance of the materials toward the ORR was analyzed by linear sweep voltammetry (LSV), rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. The main results indicate that the ORR using heteroatom-doped graphene is a direct four-electron pathway, for which the catalytic activity is higher in alkaline than in acidic media. Indeed, a change of the reaction mechanism was observed with the insertion of N into the graphenic network, by the rate determining step changes from the first electrochemical step (formation of adsorbed OOH) on glassy carbon to the removal of adsorbed O (Oad) from the N-graphene surface. Moreover, the addition of sulphur atoms into the N-graphene structure increases the catalytic activity toward the ORR, as the desorption of Oad is accelerated. [ABSTRACT FROM AUTHOR]

Metal macrocycle based non-noble metal electrocatalysts (NNMEs) with highly efficient oxygen reduction reaction (ORR) activity, good stability, and excellent resistance to the methanol cross-over effect have been regarded as one of the most important alternatives for Pt or Pt based alloys, which are widely used in fuel cells. However, the expensive price of most metal macrocycles hinder further investigation of such a family of NNMEs in large production for practical applications. Here, we introduce a simple strategy to synthesize metal macrocycle based porous carbon (MMPC) material with low cost and easy production of metal macrocycles (hemin (Hm) and vitamin B12 (VB12)) as raw materials by using a hard template of MgO. The pyrolysis of MMPC under the optimal temperature at 900 °C shows comparative ORR performance relative to commercial Pt/C, which could be attributed to the large surface area, macro-/mesoporous structure, the carbon layer encapsulating transition metal based oxides, as well as N-doped carbon species. In addition, MMPC (900) displays a better electrochemical property than 20 wt % Pt/C in terms of durability and tolerance to methanol in O2-saturated 0.1 M KOH media. [ABSTRACT FROM AUTHOR]

Oxygen reduction is considered a key reaction for electrochemical energy conversion but slow kinetics hamper application in fuel cells and metal-air batteries. In this review, the prospect of perovskite oxides for the oxygen reduction reaction (ORR) in alkaline media is reviewed with respect to fundamental insight into activity and possible mechanisms. For gaining these insights, special emphasis is placed on highly crystalline perovskite films that have only recently become available for electrochemical interrogation. The prospects for applications are evaluated based on recent progress in the synthesis of perovskite nanoparticles. The review concludes with the current understanding of oxygen reduction on perovskite oxides and a perspective on opportunities for future fundamental and applied research. [ABSTRACT FROM AUTHOR]

Low temperature fuel cells (LTFCs) are considered as clean energy conversion systems and expected to help address our society energy and environmental problems. Up-to-date, oxygen reduction reaction (ORR) is one of the main hindering factors for the commercialization of LTFCs, because of its slow kinetics and high overpotential, causing major voltage loss and short-term stability. To provide enhanced activity and minimize loss, precious metal catalysts (containing expensive and scarcely available platinum) are used in abundance as cathode materials. Moreover, research is devoted to reduce the cost associated with Pt based cathode catalysts, by identifying and developing Pt-free alternatives. However, so far none of them has provided acceptable performance and durability with respect to Pt electrocatalysts. By adopting new preparation strategies and by enhancing and exploiting synergetic and multifunctional effects, some elements such as transition metals supported on highly porous carbons have exhibited reasonable electrocatalytic activity. This review mainly focuses on the very recent progress of novel carbon based materials for ORR, including: (i) development of three-dimensional structures; (ii) synthesis of novel hybrid (metal oxide-nitrogen-carbon) electrocatalysts; (iii) use of alternative raw precursors characterized from three-dimensional structure; and (iv) the co-doping methods adoption for novel metal-nitrogen-doped-carbon electrocatalysts. Among the examined materials, reduced graphene oxide-based hybrid electrocatalysts exhibit both excellent activity and long term stability. [ABSTRACT FROM AUTHOR]

Aimed at developing a highly active and stable non-precious metal electrocatalyst for oxygen reduction reaction (ORR), a novel FexNy/NC nanocomposite--that is composed of highly dispersed iron nitride nanoparticles supported on nitrogen-doped carbon (NC)--was prepared by pyrolyzing carbon black with an iron-containing precursor in an NH3 atmosphere. The influence of the various synthetic parameters such as the Fe precursor, Fe content, pyrolysis temperature and pyrolysis time on ORR performance of the prepared iron nitride nanoparticles was investigated. The formed phases were determined by experimental and simulated X-ray diffraction (XRD) of numerous iron nitride species. We found that Fe3N phase creates superactive non-metallic catalytic sites for ORR that are more active than those of the constituents. The optimized Fe3N/NC nanocomposite exhibited excellent ORR activity and a direct four-electron pathway in alkaline solution. Furthermore, the hybrid material showed outstanding catalytic durability in alkaline electrolyte, even after 4,000 potential cycles. [ABSTRACT FROM AUTHOR]

In order to reduce the overall system cost, the development of inexpensive, high-performance and durable oxygen reduction reaction (ORR)N, Fe-codoped carbon-based (Fe/N/C) electrocatalysts to replace currently used Pt-based catalysts has become one of the major topics in research on fuel cells. This review paper lays the emphasis on introducing the progress made over the recent five years with a detailed discussion of recent work in the area of Fe/N/C electrocatalysts for ORR and the possible Fe-based active sites. Fe-based materials prepared by simple pyrolysis of transition metal salt, carbon support, and nitrogen-rich small molecule or polymeric compound are mainly reviewed due to their low cost, high performance, long stability and because they are the most promising for replacing currently used Pt-based catalysts in the progress of fuel cell commercialization. Additionally, Fe-base catalysts with small amount of Fe or new structure of Fe/Fe3C encased in carbon layers are presented to analyze the effect of loading and existence form of Fe on the ORR catalytic activity in Fe-base catalyst. The proposed catalytically Fe-centered active sites and reaction mechanisms from various authors are also discussed in detail, which may be useful for the rational design of high-performance, inexpensive, and practical Fe-base ORR catalysts in future development of fuel cells. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) is the oldest studied and most challenging of the electrochemical reactions. Due to its sluggish kinetics, ORR became the major contemporary technological hurdle for electrochemists, as it hampers the commercialization of fuel cell (FC) technologies. Downsizing the metal particles to nanoscale introduces unexpected fundamental modifications compared to the corresponding bulk state. To address these fundamental issues, various synthetic routes have been developed in order to provide more versatile carbon-supported low platinum catalysts. Consequently, the approach of using nanocatalysts may overcome the drawbacks encountered in massive materials for energy conversion. This review paper aims at summarizing the recent important advances in carbon-supported metal nanoparticles preparation from colloidal methods (microemulsion, polyol, impregnation, Bromide Anion Exchange...) as cathode material in low temperature FCs. Special attention is devoted to the correlation of the structure of the nanoparticles and their catalytic properties. The influence of the synthesis method on the electrochemical properties of the resulting catalysts is also discussed. Emphasis on analyzing data from theoretical models to address the intrinsic and specific electrocatalytic properties, depending on the synthetic method, is incorporated throughout. The synthesis process-nanomaterials structure-catalytic activity relationships highlighted herein, provide ample new rational, convenient and straightforward strategies and guidelines toward more effective nanomaterials design for energy conversion. [ABSTRACT FROM AUTHOR]

An electrochemical nanoflowers manganese oxide (MnO2) catalyst has gained much interest due to its high stability and high specific surface area. However, there are a lack of insightful studies of electrocatalyst performance in nanoflower MnO2. This study assesses the electrocatalytic performances of nanoflower structure MnO2 for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in a zinc–air battery as a bifunctional electrocatalyst. The prepared catalyst was characterized in term of morphology, crystallinity, and total surface area. Cyclic voltammetry and linear sweep voltammetry were used to evaluate the electrochemical behaviors of the as-prepared nanoflower-like MnO2. The discharge performance test for zinc–air battery with a MnO2 catalyst was also conducted. The results show that the MnO2 prepared at dwell times of 2, 4 and 6 h were nanoflowers, nanoflower mixed with nanowires, and nanowires with corresponding specific surface areas of 52.4, 34.9 and 32.4 g/cm2, respectively. The nanoflower-like MnO2 catalyst exhibits a better electrocatalytic performance towards both ORR and OER compared to the nanowires. The number of electrons transferred for the MnO2 with nanoflower, nanoflower mixed with nanowires, and nanowire structures is 3.68, 3.31 and 3.00, respectively. The as-prepared MnO2 nanoflower-like structure exhibits the best discharge performance of 31% higher than the nanowires and reaches up to 30% of the theoretical discharge capacity of the zinc–air battery. [ABSTRACT FROM AUTHOR]

The proton exchange membrane fuel cells (PEMFCs) have been considered as promising future energy conversion devices, and have attracted immense scientific attention due to their high efficiency and environmental friendliness. Nevertheless, the practical application of PEMFCs has been seriously restricted by high cost, low earth abundance and the poor poisoning tolerance of the precious Pt-based oxygen reduction reaction (ORR) catalysts. Noble-metal-free transition metal/nitrogen-doped carbon (M–NxC) catalysts have been proven as one of the most promising substitutes for precious metal catalysts, due to their low costs and high catalytic performance. In this review, we summarize the development of M–NxC catalysts, including the previous non-pyrolyzed and pyrolyzed transition metal macrocyclic compounds, and recent developed M–NxC catalysts, among which the Fe–NxC and Co–NxC catalysts have gained our special attention. The possible catalytic active sites of M–NxC catalysts towards the ORR are also analyzed here. This review aims to provide some guidelines towards the design and structural regulation of non-precious M–NxC catalysts via identifying real active sites, and thus, enhancing their ORR electrocatalytic performance. [ABSTRACT FROM AUTHOR]

A non-stoichiometric calcium titanate CaTiO3-δ (CTO) was synthesized and used as oxygen reduction reaction co-catalyst (together with Pt/C) in direct methanol fuel cells (DMFCs). A membrane-electrode assembly (MEA), equipped with a composite cathode formulation (Pt/C:CTO1:1), was investigated in DMFC, using a 2 M methanol solution at the anode and oxygen at the cathode, and compared with an MEA equipped with a benchmark Pt/C cathode catalyst. It appears that the presence of the CTO additive promotes the oxygen reduction reaction (ORR) due to the presence of oxygen vacancies as available active sites for oxygen adsorption in the lattice. The increase in power density obtained with the CTO-based electrode, compared with the benchmark Pt/C, was more than 40% at 90 °C, reaching a maximum power density close to 120 mW cm−2, which is one of the highest values reported in the literature under similar operating conditions. [ABSTRACT FROM AUTHOR]

Well-defined polyhedral Pd-Pt nanocrystals anchored on the reduced graphene oxide (rGO) are successfully synthesized via a facile and efficient surfactant-free solvothermal route. The formation mechanism is carefully illustrated via tuning the surface state of rGO substrate and the Pd/Pt ratio in Pd-Pt nanocrystals. rGO substrates with continuous smooth surface, which can offer continuous 2D larger π electrons, play important roles in the formation of the well-defined polyhedral Pd-Pt nanocrystals. Suitable Pd/Pt ratio, which determines the affinity between the rGO substrate and polyhedral Pd-Pt nanocrystals, is another important factor for the formation of polyhedral Pd-Pt nanocrystals. Due to the well-defined surface of Pd-Pt nanocrystals, rich corners and edges from polyhedral structure, as well as more exposed (111) facets, the low-Pt polyhedral Pd-Pt nanocrystals anchored on rGO, used as electrocatalysts, exhibit high electrocatalytic activity for oxygen reduction reaction with excellent methanol tolerance. [ABSTRACT FROM AUTHOR]

Large quantities of marine algae are annually produced, and have been disposed or burned as solid waste. In this work, porous carbons were prepared from three kinds of marine algae (Enteromorpha, Laminaria, and Chlorella) by a two-step activation process. The as-prepared carbon materials were doped with cobalt (Co) and applied as catalysts for oxygen reduction reaction (ORR). Our results demonstrated that Co-doped porous carbon prepared from Enteromorpha sp. (denoted by Co-PKEC) displayed excellent catalytic performance for ORR. Co-PKEC obtained a half-wave potential of 0.810 V (vs. RHE) and a maximum current density of 4.41 mA/cm2, which was comparable to the commercial 10% Pt/C catalyst (E1/2 = 0.815 V, Jd = 4.40 mA/cm2). In addition, Co-PKEC had excellent long-term stability and methanol resistance. The catalytic ability of Co-PKEC was evaluated in a one-chamber glucose fuel cell. The maximum power density of the fuel cell equipped with the Co-PKEC cathode was 33.53 W/m2 under ambient conditions, which was higher than that of the fuel cell with a 10% Pt/C cathode. This study not only demonstrated an easy-to-implement approach to prepare robust electrochemical catalyst from marine algal biomass, but also provided an innovative strategy for simultaneous waste remediation and value-added material production. [ABSTRACT FROM AUTHOR]

In this study, a low-cost and environmentally friendly method is developed to synthesize cobalt and nitrogen co-doped graphene-carbon nanotube aerogel (Co-N-GCA) as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The as-prepared Co-N-GCA has a hierarchical meso- and macroporous structure with a high N doping level (8.92 at. %) and a large specific surface area (456 m2 g−1). In an alkaline medium, the catalyst exhibits superior ORR electrocatalytic activity with an onset potential 15 mV more positive than Pt/C, and its diffusion-limiting current density is 29% higher than that of commercial Pt/C. The obtained Co-N-GCA is also highly active toward the OER, with a small overpotential of 408 mV at a current density of 10 mA cm−2. Its overall oxygen electrode activity parameter (ΔE) is 0.821 V, which is comparable to most of the best nonprecious-metal catalysts reported previously. Furthermore, Co-N-GCA demonstrates superior durability in both the ORR and the OER, making it a promising noble-metal-free bifunctional catalyst in practical applications for energy conversion and storage. [ABSTRACT FROM AUTHOR]

Exploring inexpensive and highly efficient electrocatalyst to decrease the overpotential of oxygen reduction reaction (ORR) is one of the key issues for the commercialization of energy conversion and storage devices. Heteroatom-doped carbon materials have attracted increasing attention as promising electrocatalysts. Herein, we prepared a highly active electrocatalyst, nitrogen, sulfur co-doped carbon nanofibers (N/S-CNF), via in situ chemical oxidative polymerization of methylene blue on the bacterial cellulose nanofibers, followed by carbonization process. It was found that the type of nitrogen/sulfur source, methylene blue and poly(methylene blue), has significantly influence on the catalytic activity of the resultant carbon nanofibers. Benefiting from the porous structure and high surface area (729 m2/g) which favors mass transfer and exposing of active N and S atoms, the N/S-CNF displays high catalytic activity for the ORR in alkaline media with a half-wave potential of about 0.80 V, and better stability and stronger methanol tolerance than that of 20 wt % Pt/C, indicating great potential application in the field of alkaline fuel cell. [ABSTRACT FROM AUTHOR]

In this paper, we report that WOx containing nanoalloys exhibit stable electrocatalytic performance in alkaline media, though bulk WO3 is easy to dissolve in NaOH solution. Carbon supported oxide-rich Pd–W alloy nanoparticles (PdW/C) with different Pd:W atom ratios were prepared by the reduction–oxidation method. Among the catalysts, the oxide-rich Pd0.8W0.2/C (Pd/W = 8:2, atom ratio) exhibits the highest catalytic activity for the oxygen reduction reaction. The X-ray photoelectron spectroscopy data shows that ~40% of Pd atoms and ~60% of the W atoms are in their oxide form. The Pd 3d5/2 binding energy of the oxide-rich Pd–W nanoalloys is higher than that of Pd/C, indicating the electronic structure of Pd is affected by the strong interaction between Pd and W/WO3. Compare to Pd/C, the onset potential of the oxygen reduction reaction at the oxide-rich Pd0.8W0.2/C shifts to a higher potential. The current density (mA·mg Pd−1) at the oxide-rich Pd0.8W0.2/C is ~1.6 times of that at Pd/C. The oxide-rich Pd0.8W0.2/C also exhibits higher catalytic stability than Pd/C, which demonstrates that it is a prospective candidate for the cathode of fuel cells operating with alkaline electrolyte. [ABSTRACT FROM AUTHOR]