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Search for a Platinum metal-free catalyst for Proton Exchange Membrane Fuel Cells (PEMFCs) is a concern to scientists as the Pt-catalyzed electrode comprises about 45% of the entire fuel cell stack cost. Due to layered structure, Two-dimensional (2D) MoS2 nanostructured materials have recently drawn attention as effective catalysts for oxygen reduction reaction (ORR). The 1T-phase of MoS2 (1T-MoS2) has higher electronic conductivity than the 2H-phase (2H-MoS2); high surface area 1T-MoS2 can have high electrocatalytic activity towards PEFFCs. Here, we report hydrothermally synthesized 2H-MoS2 and solvothermally synthesized mixed 1T/2H-MoS2 phases as a catalyst for ORR in PEM Fuel Cells. Owing to the high BET-specific surface area, hybrid 1T/2H-MoS2 showed better ORR activity than 2H-MoS2. The limiting current density of the 1T/2H-MoS2 hybrid structure is ‒7.1 mA cm−2 compared to Pt/C (‒8.2 mA cm−2) at 1600 rpm. The Tafel slope values of 2H-MoS2, 1T/2H-MoS2, and Pt/C are 92.7 mV dec−1, 57.5 mV dec−1, and 39.3 mV dec−1, respectively. The electron transferred during ORR are 3.8 and 1.8, respectively, for 1T/2H-MoS2 and 2H-MoS2 (in 0.1 M KOH) ; suggesting less formation of undesirable peroxide formation than 2H-MoS2. The 1T/2H-MoS2 displays better electrochemical durability compared to 2H-MoS2 (after 2000 CV cycles). [ABSTRACT FROM AUTHOR]

The efficiency and performance of proton exchange membrane fuel cells (PEMFCs) are primarily influenced by ORR electrocatalysts. In recent years, atomically dispersed metal–nitrogen–carbon (M-N-C) catalysts have gained significant attention due to their high active center density, high atomic utilization, and high activity. These catalysts are now considered the preferred alternative to traditional noble metal electrocatalysts. The unique properties of M-N-C catalysts are anticipated to enhance the energy conversion efficiency and lower the manufacturing cost of the entire system, thereby facilitating the commercialization and widespread application of fuel cell technology. This article initially delves into the origin of performance and degradation mechanisms of Fe-N-C catalysts from both experimental and theoretical perspectives. Building on this foundation, the focus shifts to strategies aimed at enhancing the activity and durability of atomically dispersed Fe-N-C catalysts. These strategies encompass the use of bimetallic atoms, atomic clusters, heteroatoms (B, S, and P), and morphology regulation to optimize catalytic active sites. This article concludes by detailing the current challenges and future prospects of atomically dispersed Fe-N-C catalysts. [ABSTRACT FROM AUTHOR]

Fe−N−C catalysts are an interesting option for polymer electrolyte fuel cells due to their low cost and high activity towards the oxygen reduction reaction (ORR). Since Fe−N−C active sites are preferentially formed in the micropores of the carbon matrix, increasing the microporosity is highly appealing. In this work, carbon xerogels (CXG) were activated by physical and chemical methods to favor the formation of micropores, used as carbon matrices for Fe−N−C catalysts, and investigated for the ORR. The catalysts were characterized by solid‐state techniques to determine chemical composition and pore structure. Physical activation increased microporosity up to 2‐fold leading to catalysts with a larger density of active sites (more than twice iron and nitrogen uptake, pyridinic N and Nx−Fe). This entailed a higher ORR intrinsic activity determined in a 3‐electrode cell (80 mV better half‐wave potential). At the cathode of a fuel cell, the catalysts based on activated carbon materials showed 26 % lower power density ascribed to a more hydrophilic surface, causing a larger extent of flooding of the electrode that counterbalances the higher intrinsic activity. Interestingly, a more stable behavior was observed for the activated catalysts, with up to 2‐fold better relative power density retention after 20‐hour operation. [ABSTRACT FROM AUTHOR]

Atomically dispersed Fe-N-C catalysts for the oxygen reduction reaction (ORR) have been synthesized with a template-free method using carbon xerogels (CXG) as a porous matrix. The porosity of the CXGs is easily tunable through slight variations in the synthesis procedure. In this work, CXGs are prepared by formaldehyde and resorcinol polymerization, modifying the pH during the process. Materials with a broad range of porous structures are obtained: from non-porous to micro-/meso-/macroporous materials. The porous properties of CXG have a direct effect on Fe-N-CXG activity against ORR in an acidic medium (0.5 M H2SO4). Macropores and wide mesopores are vital to favor the mass transport of reagents to the active sites available in the micropores, while narrower mesopores can generate additional tortuosity. The role of microporosity is investigated by comparing two Fe-N-C catalysts using the same CXG as the matrix but following a different Fe and N doping procedure. In one case, the carbonization of CXG occurs rapidly and simultaneously with Fe and N doping, whereas in the other case it proceeds slowly, under controlled conditions and before the doping process, resulting in the formation of more micropores and active sites and achieving higher activity in a three-electrode cell and a better durability during fuel cell measurements. This work proves the feasibility of the template-free method using CXG as a carbon matrix for Fe-N-C catalysts, with the novelty of the controlled porous properties of the carbon material and its effect on the catalytic activity of the Fe-N-C catalyst. Moreover, the results obtained highlight the importance of the carbon matrix's porous structure in influencing the activity of Fe-N-C catalysts against ORR. [ABSTRACT FROM AUTHOR]

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]

Finding a platinum‐free cathode catalyst that effectively models the oxygen reduction reaction (ORR) of a proton‐exchange membrane (PEM) fuel cell cathode better than the current commercial Pt/C catalyst has been a major shortcoming in fuel cell technology. Overall, a promising platinum‐free cathode catalyst must offer great ORR activity, ORR selectivity, and acid stability. Due to their enticing ORR activity and selectivity to the preferred four‐electron ORR pathway, the possible dissolution reactions and oxygen‐intermediate reactions of iron phthalocyanine monolayer supported on a pristine graphene (GFePc) and boron‐doped graphene substrate (BGFePc) have been studied to determine the stability as a function of potential and pH through spin‐polarized density functional theory (DFT) calculations at both infinitesimally low (10−9 m) and 1 m Fe2+/Fe3+ ionic concentrations. BGFePc offers higher stability in both concentrations than GFePc. In both cases, the oxygen‐intermediates are more stable than the bare catalytic surface due to the metal d‐band center shifting further away from the Fermi level in the valence band state (higher energy of antibonding). Moreover, at an Fe2+ ionic concentration, both catalysts would be stable in the potential and pH regions at the operating conditions of rotating disk electrode (RDE) experiments and PEM fuel cells. [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]

The unique chemical and physical properties of graphene and its derivatives (graphene oxide, heteroatom‐doped graphene, and functionalized graphene) have stimulated tremendous efforts and made significant progress in fuel cell applications. This review focuses on the latest advances in the use of graphene‐based materials in electrodes, electrolytes, and bipolar plates for fuel cells. The understanding of structure‐activity relationships of metal‐free heteroatom‐doped graphene and graphene‐supported catalysts was highlighted. The performances and advantages of graphene‐based materials in membranes and bipolar plates were summarized. We also outlined the challenges and perspectives in using graphene‐based materials for fuel cell applications. [ABSTRACT FROM AUTHOR]

Iron,nitrogen-codoped carbon (FeNC) has emerged as promising alternatives to precious metals for oxygen reduction reaction (ORR). Herein, we demonstrate that the ORR activity of FeNC can be markedly enhanced by the incorporation of adjacent Fe few-atom clusters (Fe AC), where the octahedral field of Fe AC boosts the splitting of the parallelogram field of FeN 4 , and facilitates the transition from high-spin (t 2g 3e g 2) Fe(III)N 4 to medium-spin (t 2g 5e g 1) Fe(II)N 4 and hence the interaction with the π* antibonding orbitals of oxygen. This leads to a remarkable ORR performance due to optimized desorption of the OH* intermediate on FeN 4 , with a half-wave potential of +0.80 in 0.1 M HClO 4 , in comparison to that with only FeN 4 single-atom moieties. In H 2 -O 2 fuel cell tests, a high peak power density of 0.80 W cm−2 is obtained. Results from this work highlight the significance of spin engineering in the manipulation and optimization of the ORR activity of single-atom catalysts. [Display omitted] • Pyrolytic treatment of Fe-doped ZIF-8 and C 3 N 4 at controlled feed ratios. • Formation of Fe few-atom clusters (Fe AC) adjacent to Fe single atom centers (Fe SA). • Transition from high-spin Fe(III)N 4 to medium-spin Fe(II)N 4 by Fe AC. • Enhanced ORR/PEMFC performance by optimized desorption of OH* on FeN 4. [ABSTRACT FROM AUTHOR]

A cathode catalyst possessing increased activity for oxygen reduction reaction (ORR) with superior durability is greatly required for polymer electrolyte membrane fuel cells (PEMFCs). Although Platinum (Pt) alloys have been widely studied for ORR, their real time application in fuel cells still remains a challenging task. Chemically ordered Pt alloys have attracted widespread attention due to the unique electronic and geometric factors that boost their electrocatalytic activity. Therefore, it is highly urgent to fabricate such ordered alloys as efficient cathode catalysts in fuel cells. Herein we report for the first time, a one-step solid-state method for the preparation of Pt 3−x Co 0.5+y Ni 0.5+y /C (x = 0, 1, 2; y = 0, 0.5, 1) nanoparticles on carbon support. Different compositions of this catalyst were studied and Pt 2 Co 1 Ni 1 /C was found to be the optimal, best performing catalyst both under half-cell and full-cell conditions. Interestingly, the mass activity of Pt 2 Co 1 Ni 1 /C was found to be seven times higher than that of commercial Pt/C in an acidic medium, achieving the Department of Energy (DOE) target for 2025. Moreover, a retention in mass activity after 50k cycles confirmed the superiority of this catalyst in effectively catalysing ORR reactions under an acidic medium. Importantly, the peak power density achieved by Pt 2 Co 1 Ni 1 /C under actual PEMFC operating conditions outperforms the commercially used Pt/C. Thus, this work provides a new approach for the simple and scalable synthesis of optimal cathode catalysts for fuel cells, opening up new dimensions in the field of energy research. • One-step solid-state method for the preparation of Pt 3−x Co 0.5+y Ni 0.5+y /C (x = 0, 1, 2; y = 0, 0.5, 1) nanoparticles. • I m of Pt 2 Co 1 Ni 1 /C found to be seven times higher than that of commercial Pt/C in an acidic medium. • Retention in mass activity after 50k cycles. • The peak power density of Pt 2 Co 1 Ni 1 /C under PEMFC conditions outperforms Pt/C. [ABSTRACT FROM AUTHOR]

Supported ordered intermetallic nanoparticles are of significant interest for catalysis applications owing to their unique surface/near-surface structures and electronic properties. However, the synthesis of small-sized intermetallic catalysts with high mass activity remains a formidable challenge, as high temperatures annealing treatments are generally requisite to achieve ordered intermetallic structures but lead to undesired larger crystallites. Here, we report an industrially relevant impregnation approach for the scalable synthesis of small-sized platinum-based intermetallic nanoparticle catalysts by regulating inter-particle distance on carbon black supports to mitigate metal sintering in high-temperature annealing. We construct a library consisting of 18 binary Pt-based intermetallic nanoparticle catalysts with an average size of < 5 nm. The prepared intermetallic catalyst libraries exhibit outstanding proton-exchange-membrane fuel cells performance, including high mass activities of 1.3–1.8 A mg Pt –1, large peak power densities of 1.2–1.4 W cm–2 in H 2 -air cells, and efficient Pt utilization of ∼0.07 g kW–1 at rated power. [Display omitted] • Intermetallic compounds (IMC) have unique strain/electronic effects in catalysis. • A family of small size Pt-based IMCs was achieved by regulating inter-particle distance. • Small size and ordered IMC structure guarantee outstanding performance in fuel cell. [ABSTRACT FROM AUTHOR]

Platinum group metal-free catalysts have been intensively investigated in the last decades as an alternative to platinum with the aim of lowering the cost of polymer electrolyte fuel cells. In particular, iron-nitrogen-carbon (Fe-N-C) has proved to be the most active towards the oxygen reduction reaction. For practical application, a hierarchical pore structure is required, with micropores favouring the creation of active sites and larger pores (meso- and macropores) facilitating the mass transport. In this work, carbon xerogels are investigated to hosting iron and nitrogen species obtained by a template-free method. The introduction of nitrogen in a one-step polymerization of urea with resorcinol and formaldehyde is investigated for the first time in this field by varying the relative content of reactants. The urea/resorcinol ratio greatly influences the pore structure of the Fe-N-C catalyst and the ORR electrocatalytic activity thereof. The ORR activity is favored for a balanced urea/resorcinol ratio where porosity is well developed and relatively high iron and nitrogen contents are incorporated to the carbon xerogel. In acid (0.5 M H 2 SO 4), the onset potential is 0.82 V vs. RHE, with a number of exchanged electrons very close to 4 (i.e. full conversion to water) and low Tafel slope of 71 mV dec−1, for the most active catalyst of the series, possessing the best compromise of iron and nitrogen active sites. Fuel cell tests corroborate that the catalyst with the most developed porous structure shows the best performance. [Display omitted] • N-doped carbon xerogels serve as carbon matrix for Fe-N-C catalysts. • Urea is introduced during gel polymerization to dope CXG with nitrogen. • A balanced urea amount leads to proper porosity including both micro and mesopores. • Pyridinic nitrogen and Fe concentration rely on N/C ratio. • High content of pyridinic N and Fe are key for enhanced ORR catalytic activity. [ABSTRACT FROM AUTHOR]

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]

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: 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]

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]

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]