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The Fe-N-C single-atom catalysts (SACs) have been widely explored for oxygen reduction reaction (ORR) in fuel cells. However, how to improve the ORR activity by tailoring the electronic structure of Fe-N-C catalysts is challenging. Herein, we synthesize a Fe-Mn-N-C dual-atom catalyst (DAC) with new local structure of FeN 4 -MnN 3 moiety, and it exhibits ultralow H 2 O 2 yield and better ORR performance than Fe-N-C and Mn-N-C SACs. Importantly, the Fe-Mn-N-C-based proton-/anion- exchange membrane fuel cells present ultrahigh power densities of 1.048 W cm−2 and 1.321 W cm−2, respectively. DFT results reveal that the strain yielded by the formation of Mn-Fe bond significantly optimizes the electronic structure of the Fe-Mn-N-C, and the co-adsorption of the Fe-Mn dual-sites for *OOH not only almost completely suppresses the 2e- ORR, but also breaks the linear correlation between G OH* and G OOH* proposed by Norskov et al., which provides a new route for the design of dual- site catalysts. [Display omitted] • Fe-Mn-N-C dual-site catalyst with FeN 4 -MnN 3 moiety exhibits ultrahigh ORR activity in acidic and alkaline media. • Fe-Mn-N-C-based PEMFC and AEMFC present ultrahigh peak power densities of 1.048 W cm−2 and 1.321 W cm−2. • DFT results reveal that the Mn-Fe bond induced strain efficiently optimizes the electronic structure of the Fe-Mn-N-C. • The co-adsorption of Fe-Mn dual-sites for *OOH almost suppresses 2e- ORR, which provides a new strategy to design catalysts. [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]

[Display omitted] • A synchronous complexation-polymerization strategy of synthesizing M−N−C electrocatalysts was developed. • As-synthesized Fe-N-C exhibits excellent ORR performance in Zn-air battery and fuel cell. • This strategy provides a flexible platform to advance molecular-level design and synthesis M−N−C catalysts. Developing atomic transition metal coordinated by nitrogen doped carbon (M−N−C) eletrocatalysts for oxygen reduction reaction (ORR) is critical to achieve low cost metal-air batteries and fuel cells. Herein, a general method of synthesizing M−N−C was developed via a synchronous complexation-polymerization strategy, in which nitrogen-containing ligand was coordinated with specific transition metal ions and diamino aromatic compound was simultaneously polymerized by the metal ion as initiator; by the following pyrolysis in a molten NaCl bath, M−N−C was finally synthesized. Fe-N-C was synthesized by this strategy using 2, 4, 6-Tri (2-pyridyl)-1, 3, 5-triazine (TPTZ) as ligand for FeCl 2 , and 1, 8-Diaminonaphthalene (DAN) as monomer of polymerization. Results demonstrate that introducing DAN into TPTZ-Fe2+ significantly affect the derived carbon structure and electrochemical performance of corresponding Fe-N-C. The Fe-N-C prepared by TPTZ and DAN with the molar ratio of 1:1 shows excellent ORR activity and durability, whose initial half-wave potential is 0.90 V in 0.1 M KOH and 0.80 V in 0.5 M H 2 SO 4 respectively, after 10 K cycles, the potential is only 14 mV loss in 0.1 M KOH and 20 mV decay in 0.5 M H 2 SO 4. And the ORR performance as cathode is further proved by a single practical Zn-air battery with a maximum power density of 192 mW cm−2 and a specific capacity of 800 mAh g Zn -1, much higher than 137 mW cm−2 and 735 mAh g Zn -1 of the same loading of commercial Pt/C catalyst and proton exchange membrane fuel cell with a high power output of 640 mW cm−2. Attributed to the vast kinds of ligands, metal ions and polymerizing monomers, this strategy provides a flexible platform of synthesizing advanced M−N−C catalysts, compared with other reported methods. [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]

Highlights: [•] Good performance is obtained for PtCo alloy/Ta-doped Ti-oxide for ORR in PEMFCs. [•] High electrochemical stability is shown by PtCo/Ta-doped Ti-oxide at 1.4V RHE. [•] Oxide support shows promoting effect for ORR at intermediate temperatures (110°C). [•] Higher performance is achieved with Pt–Co/oxide vs. Pt/oxide in PEMFCs. [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]

• Atomically dispersed bimetallic FeCu coordinated with N-CNTs, FeCu/N-CNTs, are developed. • FeCu/N-CNTs show PA enhance activity and stability for ORR at elevated temperatures. • PA/PBI cells based on FeCu/N-CNTs cathode show a high and stable power performance at 230 degrees. • DFT calculation verifies the promotion mechanism of phosphate on bimetallic FeCu for ORR. Phosphate poisoning of Pt electrocatalysts is one of the major barriers that constrains the performance of phosphoric acid-doped polybenzimidazole (PA/PBI) membrane fuel cells. Herein, we developed new atomically dispersed bimetallic FeCu coordinated with nitrogen-doped carbon nanotubes (FeCu/N-CNTs) as Pt-free oxygen reduction reaction (ORR) electrocatalysts. The cell with FeCu/N-CNTs cathodes delivers a peak power density of 302 mWcm−2 at 230℃, similar to that using Pt/C electrocatalysts (1 mg Pt cm−2) but with a much better stability. In contrast to phosphate poisoning of Pt/C, FeCu/N-CNTs show PA enhanced activities. DFT calcualtions indicate that phosphate promotion effect results from the stronger binding of phosphate on Cu sites, which decreases the activation energy barrier for the cleavage of the O 2 double bond and provides local protons to facilitate the proton-coupled electron transfer ORR. The results also show that FeCu/N-CNTs have a much better activity for ORR as comapre to Fe single atom catalysts coordinated with nitrogen-doped carbon nanotubes, Fe/N-CNTs. This study demonstrates the promising potential of bimetallic FeCu/N-CNTs as true Pt-free, highly active and durable cathodes for PA/PBI based high temperature polymer electrolyte fuel cells. [ABSTRACT FROM AUTHOR]

• Carbon-supported Pt-based materials with Matryoshka-like structure are proposed as ORR catalysts. • The catalyst has 3.4 times higher mass activity than commercial Pt/C in half-cell. • Pt@Cu IL Pd/C-based polymer electrolyte membrane fuel cells show high and stable performance. Electrochemical catalysts with a core-shell structure have received much attention because of their enhanced efficiency and activity. Among them, those with a CuPd alloy core exhibit better activity than the ones with a single metal Pd core, which is known to be an excellent core-material. However, the superior performance of previously reported Pt catalysts with CuPd core has only been observed in half-cells, and was not reflected or even expanded to single-cells. We report catalysts having a Matryoshka-like structure with a Pt outer-layer, Cu interlayer, and Pd core for oxygen reduction reaction. This catalyst has 3.4 times higher Pt mass activity than the commercial Pt/C in half-cells, and also performs better in single-cells at only 0.056 mg Pt cm−2. Particularly, the stability of this catalyst satisfies the 2020 DOE target, and electrochemical surface area loss during the stability test is only 40 % for this catalyst, while that of Pt/C is 80 %. [ABSTRACT FROM AUTHOR]

• Method for rapid and comparable catalyst layer evaluation developed. • Successful benchmark experiments with commercial Fe-N-C catalyst and alkaline ionomer. • Optimized cathode performance after pre-conditioning for 48 h in 1 M KOH. • Fe-N-C catalyst layers show very high stability after 5000 cycles between 0.6 and 1.0 V vs. RHE. Anion exchange membrane fuel cells (AEMFC) are a promising technology to allow the application of non-precious metal catalysts. While many of such catalysts have been identified in numerous recent fundamental research studies, reports evaluating these catalysts in realistic AEMFC catalyst layers together with stability assessments are rare. In the present work we show that fast and reliable evaluation and optimization of Fe-N-C-based oxygen reduction reaction (ORR) catalyst layers can be achieved using a gas diffusion electrode (GDE) half-cell approach. To set a benchmark in such measurements, a commercial Pajarito Powder Fe-N-C catalyst and commercial AemionTM ionomer are used. It is demonstrated that the ORR performance can be increased significantly by fine-tuning of the ionomer activation time. Furthermore, the optimized Fe-N-C-based catalyst layer shows very high stability with no observable performance deterioration after 5000 cycles in the 0.6–1.0 V vs. RHE potential window. [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]

Developing the optimized electrocatalysts with high Pt utilization as well as the outstanding performance for the oxygen reduction reaction (ORR) has raised great attention. Herein, the effects of the interlayer ZrC, HfC, or TiN and the multilayer Pt shell on the adsorption ability and the catalytic activity of the TiC@Pt core-shell structures are systemically investigated by density functional theory (DFT) calculations. For the sandwich structures, the presence of TiN significantly enhances the adsorption ability of the Pt shell, leading to the deterioration of the activity whilst the negligible influence of the ZrC and HfC insertion results the comparable performance with respect to TiC@Pt1ML. In addition, increasing the thickness of the Pt shell reduces the oxyphilic capacity and then mitigates the OH poisoning. From the free energy plots, the superior activity of TiC@Pt2ML is identified in comparison with 1ML and 3ML Pt shell. Herein, the improved activity with its high Pt atomic utilization makes the potential TiC@Pt2ML electrocatalyst for the future fuel cells. [ABSTRACT FROM AUTHOR]

Oxygen-depolarized cathodes are a novel concept to be used in chlor-alkali electrolysis in order to generate significant energy savings. In these porous gas diffusion electrodes, hydrophilic and catalytically active microsized silver grains and a hydrophobic polytetrafluoroethylene cobweb structure are combined to obtain the optimum amount of three-phase boundaries between the highly alkaline electrolyte and the oxygen gas phase to achieve high current densities. However, the direct correlation between specific electrode structure and electrochemical performance is difficult. In this work, we report on the successful design and adaptation of an in-operando cell for X-ray (micro-computed tomography, synchrotron) and neutron imaging of an operating oxygen-depolarized cathode under realistic operation conditions, enabling the investigation of the electrolyte invasion into, and distribution inside, the porous electrode for the first time. [ABSTRACT FROM AUTHOR]

In this paper, a numerical model of the kinetic Monte Carlo (KMC) method has been developed to study the oxygen reduction reaction (ORR) that occurs inside the cathode catalyst layer (CCL). Firstly, a 3-D model of the CCL that consists of Pt and carbon spheres is built using the sphere packing method; secondly, an efficient procedure of the proton-oxygen reaction process is developed and simulated. In the proton-oxygen reaction process, all of the continuous movements of protons and oxygen are considered. The maximum reaction distance is determined to be 8 Å. The input pressures of protons and oxygen are represented by the number of spheres of the species. The value of the current density is calculated based on the amount of reaction during the interval time. Indications are that the results of the present model match reasonably well with the published results. A new way to apply the KMC method in the proton exchange membrane fuel cell (PEMFC) research field is developed in this paper. [ABSTRACT FROM AUTHOR]