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Abstract The exploration of cheap and stable electrocatalysts with high activity towards oxygen reduction reaction in the acidic and alkaline medium is a vital activity for large-scale applications of fuel cells. In recent years, one-dimensional nanofibrous electrode materials with high surface area and specific porosities have been drawing great attention in energy conversion devices such as fuel cells and metal-air batteries. Nanofibers with a one-dimensional nanostructure can be produced by electrospinning, which has been considered as a particularly low-cost and versatile method. In this review, we summarize the properties of electrospun nanofibers and the recent progress in designing of non-precious nanostructured electrocatalysts for oxygen reduction reaction in fuel cells. More importantly, we also highlight the interesting nanostructures, new synthetic approaches, and the electrocatalytic performance including active sites and stability of electrospun-based electrocatalysts. In addition, we describe the research challenges and future developmental perspectives of electrospun materials in energy technology. Highlights • Non-precious nanostructured electrocatalysts by electrospinning are summarized. • The active sites and reaction mechanism of the electrocatalysts are discussed. • Research challenges and future perspectives are described. [ABSTRACT FROM AUTHOR]

Abstract Presently, the practical application of Fe/N/C catalysts as replacements of Pt for oxygen reduction reaction is still limited by insufficient activity. Herein, we demonstrate a novel design for such catalyst. On one hand, the obtained Fe/N/C SiO 2 ZnCl 2 catalyst owns high densities of well-exposed active-sites derived from three-dimensional well-balanced macro-, meso-, and microporous structures constructed by adopting ZnCl 2 salt and SiO 2 microspheres as combined templates. On the other hand, simulation reveals that a high loading of catalyst in cathode catalyst layer would not benefit cell performance and fast oxygen reduction reaction process occurs only inside a limited thickness of catalyst layer. Particularly, the Fe/N/C SiO 2 ZnCl 2 shows a maximal output power density as high as 480 mW cm−2 at an ultra-low loading of 0.5 mg cm−2. This study firstly exhibits that development of catalysts with high-density active sites and construct of ultra-thin catalyst layer are of great significance for improving the performance of fuel cell. Highlights • Fe/N/C SiO 2 ZnCl 2 was synthesized using ZnCl 2 templating and silica templating. • Fe/N/C SiO 2 ZnCl 2 shows superior ORR activity in both alkaline and acidic medium. • The P max of Fe/N/C SiO 2 ZnCl 2 is as high as 480 mW cm−2 at a 0.5 mg cm−2 loading. [ABSTRACT FROM AUTHOR]

Metal-nitrogen-carbons (M-N-Cs) as a reliable substitution for platinum-group-metals (PGMs) for oxygen reduction reaction (ORR) are emerging candidates to rationalize the technology of fuel cells. The development of M-N-Cs can further be economized by consuming waste biomass as an inexpensive carbon source for the electrocatalyst support. Herein, we report the simple fabrication and in-depth characterization of electrocatalysts using lignin-derived activated char. The activated char (LAC) was functionalized with metal phthalocyanine (FePc and MnPc) via atmosphere-controlled pyrolysis to produce monometallic M-N-Cs (L_Mn and L_Fe) and bimetallic M1-M2-N-Cs (L_FeMn) electrocatalysts. Raman spectroscopy and transmission electron microscopy (TEM) revealed a defect-rich architecture. XPS confirmed the coexistence of various nitrogen-containing active moieties. L_Fe and L_FeMn demonstrated appreciable ORR in both acidic and alkaline conditions whereas L_FeMn helped in restricting the peroxide yield, particularly in alkaline media. L_Fe and L_FeMn demonstrated remarkable onset potential (E onset) of ∼0.942 V (vs RHE) with an E 1/2 of 0.874 V (vs RHE) in 0.1 M KOH. In acid, L_FeMn had an E onset of 0.817 V (vs RHE) and an E 1/2 of ∼0.76 V (vs RHE). Finally, the L_FeMn as a cathode electrocatalyst was integrated and tested in PEMFC and AEMFC. AEMFC demonstrated optimistic performance with a peak power density of 261 mW cm−2 at the current density of ∼577 mA cm−2. • Waste lignin was valorized through pyrolysis and high surface area char was synthesized. • The biochar was functionalized by Fe-, Mn- and Fe–Mn phthalocyanine. • Fe- and FeMn- catalysts showed superior ORR compared to Mn-catalyst. • Integration of PGM-free FeMn-catalyst in PEMFC reached a P max of ∼72 mW cm−2. • Integration of PGM-free FeMn-catalyst in AEMFC reached a P max of ∼261 mW cm−2. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks were used as metal-nitrogen-carbon templates to synthesize Co–N–C catalysts through a facile synthesis approach that combined a cobalt-based zeolitic imidazolate framework (ZIF) structure and conductive carbon support. The spectroscopic, structural, and thermogravimetric analysis confirmed the synthesis of the Co-based ZIF, used to prepare catalysts with different ZIF/carbon support ratios by pyrolysis under inert atmosphere. Electrochemical characterization at alkaline pH demonstrated high activity towards oxygen reduction reaction (ORR). In addition to ORR activity, the Co–N–C electrocatalysts showed high methanol tolerance in the preliminary tests in a half-cell configuration. When assembled at the cathode side of both a hydrogen-fed anion exchange membrane fuel cell and an alkaline direct methanol fuel cell (ADMFC), the Co–N–C electrocatalysts showed competitive performance with the state-of-the-art Pt/C and other platinum-group-metal-free materials, using a FUMASEP® FAA-3-50 membrane. Exceptionally high performance (higher than 45 mW cm−2) was achieved in ADMFC fed with high methanol concentration (up to 10 M), due to the high methanol tolerance of Co–N–C electrocatalysts. Normalizing the performance to Pt loading, a value of 31.0 mW mg Pt −1 was obtained, which is the highest power up to now recorded with this kind of membrane and one of the highest values in the literature for ADMFCs. [Display omitted] • Metal-organic-framework-derived Co–N–C electrocatalysts. • High catalytic activity towards oxygen reduction in an alkaline environment. • Remarkable methanol tolerance of Co–N–C electrocatalysts. • Application in H 2 -fed anion exchange membrane fuel cells cathodes. • Application in alkaline direct methanol fuel cells cathodes with high power output. [ABSTRACT FROM AUTHOR]

The distribution of platinum group metal (PGM) nanoparticle catalysts throughout the porous structure of the carbon support has been widely reported to have a significant impact on the performance of the catalyst. For catalysts having Pt primarily on the outer surface of the carbon, low mass activity but excellent performance at high current densities is often observed. Conversely, when Pt is deposited within the pores of the carbon, high mass activity but poor performance at high current density is observed. This relationship has been well studied, and the mechanism has been clearly elucidated. A key method in the literature to study Pt distribution has been the 'Pt accessibility' tests, which are based on monitoring roughness factor (cm2Pt/cm2 membrane electrode assembly (MEA)) vs. relative humidity (RH). While these tests have now been correlated with performance, most of the polarization testing during these studies is performed under one single RH condition. In this work, the relationship between Pt spatial distribution and RH tolerance is probed to gain further insight into how the materials-level properties of the catalyst impact MEA-level characteristics. This work provides an additional design tool that can be used by MEA designers when selecting catalysts for their specific application. [Display omitted] • Study of relative humidity tolerance as a function of Pt spatial distribution. • New mechanism proposed to explain the relative humidity/performance relationship. • Recommendations provided for the design and selection of Pt/C catalysts. [ABSTRACT FROM AUTHOR]

Low-cost, high-performances and durable hydrogen fuel cells are crucial for the success of the hydrogen economy. While Fe–N–C structures containing Fe-N x active sites are amongst the most promising platinum (Pt)-group metal (PGM)-free catalysts for the oxygen reduction reaction, their highest performances-to-date are still inferior to commercial Pt in real proton exchange membrane fuel cells. Herein, we shed light on this performance gap by using the distribution of relaxation times to quantify the proton transport and oxygen reduction reaction kinetics of a high-performance Fe–N–C catalyst (1.08 W cm−2) and a commercial Pt catalyst (1.7 W cm−2) in hydrogen fuel cell. This study unveils that the Fe–N–C catalyst has slower proton transport and oxygen reduction reaction kinetics than Pt as the Fe–N–C nanoporous carbon matrix limits active site accessibility. Furthermore, while increasing the Fe–N–C catalytic mass loading (from 1 to 3 mg Fe-N-C cm−2) enhances the power density in hydrogen fuel cells, it also slows down proton transport and oxygen reduction reaction kinetics by lengthening the gas, electron, and proton pathways to the active sites. This finding will drive the development of PGM-free catalysts for hydrogen fuel cells and of single-atom catalysts for electrochemical applications. [Display omitted] • The distribution of relaxation times captures ORR kinetics of PGM-free catalysts. • PGM-free catalysts nanoporous structure reduces ORR and proton transport kinetics. • Using high loadings of PGM-free catalysts increases the pathway to active sites. [ABSTRACT FROM AUTHOR]

A new platinum group metal (PGM)-free proton exchange membrane fuel cell (PEMFC) cathode catalyst materials, synthesized using the VariPore™ method by Pajarito Powder, LLC, are characterized for their structure and activity. The physico-chemical analysis of the iron-nitrogen-carbon (Fe-N-C) electrocatalysts show mesoporous carbon material effectively doped with iron and nitrogen. The materials have an average pore size of 7–8 nm and high specific surface area. The Fe-N-C catalysts exhibit good oxygen reduction reaction (ORR) activity in 0.5 M H 2 SO 4 electrolyte with high half-wave potential and sustainable electrochemical stability over 10,000 repeated potential cycles with insignificant losses in their activities. As cathode catalysts in a PEMFC, the Fe-N-C materials deliver remarkably good fuel cell performance at low overpotential approaching that of the commercial Pt catalyst. The high ORR electrocatalytic activity of these Fe-N-C catalysts is credited to the synergy between nitrogen-moieties, specifically pyrrolic-N, pyridinic-N, and graphitic-N, and iron in addition to the high mesoporosity that facilitate an effective reaction path in boosting the electrocatalytic activity and stability. [Display omitted] • State-of-the-art commercial PGM-free catalysts for ORR were characterized and evaluated. • Was shown that active centres are atomically dispersed. • Performance of electrocatalysts was evaluated in industrially manufactured MEA form-factor. • The fuel cell performance is close to the state-of-the-art R&D PGM-free catalysts. [ABSTRACT FROM AUTHOR]

Abstract: The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction is severely poisoned. Poisoning at the cathode explains the majority of the losses observed in polymer electrolyte membrane fuel cells contaminated with ammonia. Voltammetry in deaerated solution suggest that the poisoning can be attributed to either ammonium oxidation or increased binding to OH species. [Copyright &y& Elsevier]

Abstract: In this study, a novel core–shell structured Pd3Fe@Pt/C electrocatalyst, which is based on Pt deposited onto carbon supported Pd3Fe nanoparticles, is prepared for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). The carbon supported Pd3Fe nanoparticles act as seeds to guide the growth of Pt. The formation of the core–shell structured Pd3Fe@Pt/C is confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical characterization. The higher surface area of the synthesized catalyst suggests that the utilization of Pt in the Pd3Fe@Pt/C catalyst is higher than that in Pt/C. Furthermore, better electrocatalytic performance than that of Pt/C and Pd3Fe/C catalyst is observed in the ORR which follows a four-electron path. Consequently, the results indicate that the Pd3Fe@Pt/C catalyst could be used as a more economically viable alternative for the ORR of PEMFCs. [Copyright &y& Elsevier]

Abstract: A solution-phase synthesis method was studied to prepare carbon supported Pt-Co alloy catalysts. The organic precursors of Pt acetylacetonate and Co acetylacetonate were reduced in a high boiling point solvent of octyl ether in the presence of oleic acid (OAc) and oleylamine (OAm) to produce fine Pt-Co nanoparticles, which were subsequently deposited on carbon support to obtain Pt-Co/C catalysts. Thermogravimetric analysis suggests that the stabilizers (OAc and OAm) can be removed by copious ethanol washing and subsequent moderate temperature heat-treatment (250°C, under Argon atmosphere). X-ray diffraction patterns indicate that the average particle size is around 2.3nm, and the lattice parameter is 3.868Å for the heat-treated Pt-Co/C (40wt%). Transmission electron microscopy images show very small Pt-Co alloy nanoparticles homogeneously dispersed on the carbon support with a particle size distribution of 2–4nm for all Pt-Co/C samples. The elements composition of Pt and Co in the final Pt-Co/C catalyst can be well controlled, as evidenced by inductively coupled plasma atomic emission spectroscopy and energy dispersive spectroscopy analyses. Proton exchange membrane fuel cell tests show the heat-treated Pt-Co/C cathode catalyst has higher mass activity of oxygen reduction reaction than Pt/C at an operation voltage of 0.9V, this can be attributed to its smaller particle size and reduced lattice parameter. [Copyright &y& Elsevier]

This paper deals with the performance analysis of a proton exchange membrane fuel cell in automotive applications and especially for start/stop phases. Start-Stop cycles are one of the main sources of degradation for fuel cell systems, embedded in the automotive applications, among other dynamic conditions as idling, load cycling or high power. In this study, polarization curves and electrochemical impedance spectra are used to analyze the degradation mechanisms inside fuel cell stack during start/stop cycling. Obviously, the carbon support of the catalyst layer is the main constituent that suffers performance degradation during the 2,600 successive cycles performed. The impedance measurement of a 5 kW PEM fuel cell stack revealed that the ohmic resistance does not vary whereas the charger transfer and mass transfer resistances increase drastically depending on the number of cycle repetitions. The oxygen reduction reaction impact due to the fuel/air interface is also visible even if the reactants are consumed with a dummy load for the shutdowns. • 2,600 repetitive start/stop cycles are performed on a 5 kW PEM fuel cell stack. • The degradation behavior of a fuel cell during start/stop cycling is evaluated. • The effects of calendar aging during long resting time are investigated. • Shutdown strategy is based on reactants consumption by using a dummy load. • The degradation mechanisms associated to fuel/air interface are observed. [ABSTRACT FROM AUTHOR]

Ceria coated carbon nanotubes (CeO 2 @CNTs) were prepared as a versatile support material to improve both the activity and stability of platinum (Pt)-based catalysts. We demonstrated that the CeO 2 nanoparticles (NPs) had an extrinsically remote functionalization effect on the Pt electrocatalysis. The CeO 2 modulated the electronic structure, and facilitated the O 2 adsorption property of Pt without any intrinsic chemical doping or Pt-alloying. This led to d -band electron filling in Pt, and delivery of active oxygens (O−) to the Pt surface via oxygen spillover at the Pt-CeO x interface, thus enhancing the ORR activity. Furthermore, due to the unique redox behavior between Ce3+ and Ce4+, the dissolved Ce ions could also participate in the radical scavenge reaction, which prevents the chemical degradation of polymeric components in the cell. A single cell using the Pt NPs supported on CeO 2 @CNT as a cathode catalyst delivered a superior electrochemical performance and a retained durability compared to the cells with pristine CNT supported Pt NPs. • The ceria functionalized Pt/CNT (Pt@CeO 2 @CNT) was used as PEM fuel cell catalysts. • Ceria improves the ORR activity of adjacent Pt nanoparticles catalyst. • Dissolved Ce ions effectively scavenge the oxidative free radicals. • Pt@CeO 2 @CNT exhibits outstanding activity and stability in PEM fuel cells.. [ABSTRACT FROM AUTHOR]

Proton exchange membrane fuel cells (PEMFCs) attract immense interest recently; however, the activity and usage amount of the Pt nanoparticles therein pose limitations to their application. We synthesize highly active and durable Pt nanoparticles for the electrocatalytic oxygen reduction reaction (ORR) in fuel cells. In the presence of an S-containing surfactant during the synthesis, the Pt nanoparticles are strongly anchored to the catalyst support, which results in narrow size distribution. Successive heat treatment under reducing conditions provides an S-doped carbon structure as a functional layer of Pt/C, thereby enhancing the durability. The functional layers are able to facilitate the rate-determining step of the ORR by lowering the OOH coverage. The PEMFC power density similar to that of pristine Pt/C achieves using only half Pt amount at the cathode due to the synergetic effect of Pt and S-doped carbon. Image 1 • Improved activity toward oxygen reduction on Pt NPs covered by S-doped carbon layer. • Surfactant fosters both uniform Pt distribution and creation of a thin carbon layer. • High PEMFC performance with ultra-low Pt incorporated in S-doped carbon layer. [ABSTRACT FROM AUTHOR]

Stable hybrid silica decorated carbon composite is realized for improving oxygen reduction kinetics, performance and stability of polymer electrolyte fuel cell. Synthesis of platinum on an optimum level of silica decorated into carbon via single-step polyol method with minimum loading of platinum (0.15 mg cm−2) shows superior power density of 1.45 W cm−2 in relation to platinum on carbon. The optimum composition of silica decorated carbon preserves 70% of the electrochemical active surface area of platinum even after 6000 cycles from 1 to 1.5 V. The water retention ability for silica is responsible for maintaining the humidity within the triple phase boundary of the membrane electrode assembly, which in turn increases the fuel cell performance and stability even up to 100 h under low humidity. Besides, air-cooled prototype 15 cell stack is assembled comprising the above electrocatalyst which exhibits the power output of 100 W at 10 V under 40% relative humidity. Image 1 • Silica-decorated carbon-Pt electrocatalyst is synthesized. • Pt/CS 3 electrocatalyst show higher oxygen reduction activity. • Pt/CS 3 electrocatalyst show higher PEFC performance under low humidity. • Pt/CS 3 electrocatalyst shows enhanced stability when compared with Pt/C. • 15 cell stack comprising Pt/CS 3 catalyst is also explored under low humidity. [ABSTRACT FROM AUTHOR]