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An oxygen reduction reaction (ORR) is the key half reaction of proton exchange membrane fuel cells (PEMFCs), and is highly dependent on Pt-based nanocrystals as core electrocatalysts. Despite the exceptional ORR activity from adjusting the electronic structures of surface or near-surface atoms, several serious issues, including the corrosion of carbon supports, the preferential leaching of active metal elements, the instability of surface low-coordinated atoms and the sintering/agglomeration of nanocrystals, still exist, challenging the ORR durability of developed Pt-based ORR catalysts. From the point of view of the catalyst structure design, in this review, we summarized the state-of-the-art structural regulation strategies for improving the ORR durability of Pt-based catalysts. The current limitation of Pt-based binary catalysts for ORR electrocatalysis is firstly discussed, and the detailed strategies are further classified into the optimization of supports, metal-doped alloys, core/shell structures, intermetallics and high-entropy alloys, etc. The structure–performance relationship is detailedly explained, especially emphasizing the elimination of the above restrictions. Finally, the existing challenges and future research direction are further presented, aiming at practicing the PEMFC devices of the ultradurable Pt-based catalysts. [ABSTRACT FROM AUTHOR]

The advancement of efficient and stable single-atom catalysts (SACs) has become a pivotal pursuit in the field of proton exchange membrane fuel cells (PEMFCs) and metal-air batteries (MABs), aiming to enhance the utilization of clean and sustainable energy sources. The development of such SACs has been greatly significant in facilitating the oxygen reduction reaction (ORR) process, thereby contributing to the progress of these energy conversion technologies. However, while transition metal-based SACs have been extensively studied, there has been comparatively less exploration of SACs based on p-block main-group metals. In this study, we conducted an investigation into the potential of p-block main-group Sn-based SACs as a cost-effective and efficient alternative to platinum-based catalysts for the ORR. Our approach involved employing density functional theory (DFT) calculations to systematically examine the catalyst properties of Sn-based N-doped graphene SACs, the ORR mechanism, and their electrocatalytic performance. Notably, we employed an H atom-decorated N-based graphene matrix as a support to anchor single Sn atoms, creating a contrast catalyst to elucidate the differences in activity and properties compared to pristine Sn-based N-doped graphene SACs. Through our theoretical analysis, we gained a comprehensive understanding of the active structure of Sn-based N-doped graphene electrocatalysts, which provided a rational explanation for the observed high four-electron reactivity in the ORR process. Additionally, we analyzed the relationship between the estimated overpotential and the electronic structure properties, revealing that the single Sn atom was in a +2 oxidation state based on electronic analysis. Overall, this work represented a significant step towards the development of efficient and cost-effective SACs for ORR which could alleviate environmental crises, advance clean and sustainable energy sources, and contribute to a more sustainable future. [ABSTRACT FROM AUTHOR]

In this study, ex situ and operando X‐ray absorption spectroscopy (XAS) is employed to shed light on structure and degradation mechanism of Fe‐based catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Ex situ XAS on pristine Fe0.07Zr0.93O2‐δ/C catalyst confirms the incorporation of Fe3+ in the ZrO2 structure and clearly exclude any significant presence of Fe−N−C‐type structures. The edge shift in data on in‐house aged samples demonstrates a mixed oxidation state of Fe (Fe3+ and Fe2+), consistent with Fe demetalation from the ZrO2 structure. Furthermore, a more symmetric coordination in the pre‐edge shape points towards the formation of oxidic Fe clusters upon aging. Fe demetalation is inferred also from the edge shift to higher energy (presence of Fe3+) in operando XAS data at 0.3 V, due to Fe phases not electrically polarizable/reducible at the applied voltage. Electrochemical data exclude any correlation between extent of aging and type of test, also for a commercial Fe−N−C catalyst by Pajarito Powder. The observed faster aging for Fe0.07Zr0.93O2‐δ compared to Fe−N−C is attributed to an improved mass transport to/from active sites, manifest also in very similar initial current densities at 0.3 V, despite much higher catalyst activity for Fe−N−C. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) is a very important reaction that occurs at the cathodic side in proton exchange membrane fuel cells (PEMFCs). The high cost associated with frequently used Pt-based electrocatalysts for ORR limits the commercialization of PEMFCs. Through bifunctional and electronic effects, theoretical calculations have proved that alloying Pt with a suitable transition metal is likely to improve ORR mass activity when compared to Pt-alone systems. Herein, we demonstrate the preparation of bimetallic Pt–Fe nanoparticles supported on reduced graphene oxide sheets (RGOs) via a simple surfactant-free chemical reduction method. The present method produces PtFe/RGO catalyst particles with a 3.2 nm diameter without agglomeration. PtFe/RGO showed a noticeable positive half-wave potential (0.503 V vs. Ag/AgCl) compared with a commercial Pt/C catalyst (0.352 V vs. Ag/AgCl) with minimal Pt-loading on a glassy carbon electrode. Further, PtFe/RGO showed a higher ORR mass activity of 4.85 mA/cm2-geo compared to the commercial Pt/C (3.60 mA/cm2-geo). This work paves the way for designing noble−transition metal alloy electrocatalysts on RGO supports as high-performance electrocatalysts for ORR application. [ABSTRACT FROM AUTHOR]

The highly efficient energy conversion of the polymer‐electrolyte‐membrane fuel cell (PEMFC) is extremely limited by the sluggish oxygen reduction reaction (ORR) kinetics and poor electrochemical stability of catalysts. Hitherto, to replace costly Pt‐based catalysts, non‐noble‐metal ORR catalysts are developed, among which transition metal–heteroatoms–carbon (TM–H–C) materials present great potential for industrial applications due to their outstanding catalytic activity and low expense. However, their poor stability during testing in a two‐electrode system and their high complexity have become a big barrier for commercial applications. Thus, herein, to simplify the research, the typical Fe–N–C material with the relatively simple constitution and structure, is selected as a model catalyst for TM–H–C to explore and improve the stability of such a kind of catalysts. Then, different types of active sites (centers) and coordination in Fe–N–C are systematically summarized and discussed, and the possible attenuation mechanism and strategies are analyzed. Finally, some challenges faced by such catalysts and their prospects are proposed to shed some light on the future development trend of TM–H–C materials for advanced ORR catalysis. [ABSTRACT FROM AUTHOR]

Platinum has been considered as an essential element in both the cathode and anode catalyst in Proton Exchange Membrane Fuel Cells (PEMFC). However, with the increasing capacity of PEMFC industry in both transportation and stationary applications, the demand for platinum increases rapidly. From the standpoint of scarcity and cost, developing platinum group metal free (PGM-free) catalyst is rewarding. In this work, we prepared highly active material with secondary nitrogen doping, and were able to scale up material synthesis from milligram scale to gram scale with the high activity well maintained. The scale up catalyst SU-PAU was evaluated in 50 cm2 MEAs with comprehensive operating and design parameter optimization. The state of art 670 mW/cm2 peak power density was achieved under H 2 -Air operation, with the air partial pressure of 1 bar. • Fe–N–C family PGM-free ORR catalyst synthesis is scaled up from milligram sale to gram scale. • Secondary nitrogen doping creates more micropores and increases ORR activity. • Performance of 50 cm2 MEAs are studied with a variety of testing and design parameters. • State of art PGM-free catalyst based H 2 -Air performance (670 mW/cm2) is achieved. [ABSTRACT FROM AUTHOR]

In order to decrease the cost and enhance the performance of the cathode catalyst for PEMFC, carbon supported PtCu and PtCuAg alloys with differential Ag content are synthesized by a borohydride chemical reduction. The oxygen reduction reaction (ORR) activity are tested by cyclic voltammetry (CV）and linear sweep voltammograms (LSV) in 0.5 M H 2 SO 4 . By comparison with the ORR activities of PtCu/C and a series of PtCuAg/C catalysts with differential metal atomic ratios of Pt:Cu:Ag, the PtCuAg/C catalyst with the atomic ratio on 3:10:1 (marked as PtCuAg/C(3:10:1)) shows the best catalytic activity. For the 200th cycles, the limited current reaches to 3.85 mA cm −2 for PtCuAg/C(3:10:1) with Pt-loading of 9.29 μg Pt cm −2 . The CV curves of the PtCuAg/C catalysts show one more pair of redox peaks of Ag compared with PtCu/C catalyst, which is much different from Pt-M alloy catalysts reported in other literature. The TEM and XRD as well as XPS results indicate that the enhanced ORR activity is the result of the smaller particle size, the crystal distortion and the more exposure of Pt atoms with the introduction of Ag for PtCuAg/C(3:10:1) catalyst. [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 iridium oxide nanoparticles supported on Vulcan XC-72 porous carbon were prepared for cathode catalyst in polymer electrolyte fuel cell (PEFC). The catalyst has been characterized by transmission electron microscopy (TEM) and in PEFC tests. The iridium oxide nanoparticles, which were uniformly dispersed on carbon surface, were 2–3nm in diameter. With respect to the oxygen reduction reaction (ORR) activity was also studied by cyclic voltammetry (CV), revealing an onset potential of about 0.6V vs. an Ag/AgCl electrode. The ORR catalytic activity of this catalyst was also tested in a hydrogen–oxygen single PEFC and a power density of 20mWcm−2 has been achieved at the current density of 68.5mAcm−2. This study concludes that carbon-supported iridium oxide nanoparticles have potential to be used as cathode catalyst in PEFC. [Copyright &y& Elsevier]

Abstract: Pd45Pt5Sn50 electrocatalyst was prepared by a NaBH4 reduction of PdCl2, H2PtCl6 and SnCl2 in THF at 0°C. This catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) microanalysis and hydrodynamic electrochemical technique. XRD, SEM and TEM results demonstrate that the borohydrate reduction methodology enable the synthesis of conglomerated particles nanometric in size ranging from 1 to 6nm. Oxygen reduction reaction (ORR) activity was investigated on carbon dispersed catalyst by rotating disk electrode (RDE) technique in H2SO4 0.5M. The effect of temperature on the kinetics was analyzing resulting in an apparent activation energy of 42.54±1kJmol−1, value which is less than the obtained for the nanostructured bimetallic PdSn electrocatalyst under the same experimental condition. The Pd45Pt5Sn50 electrocatalyst dispersed on a carbon powder was tested as cathode electrocatalyst in a membrane-electrode assembly (MEA) arriving to a power density of 210mWcm−2 at 0.35V and 80°C. [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]