Search

Platinum-based intermetallic compounds (IMCs) play a vital role as electrocatalysts in a range of energy and environmental technologies, such as proton exchange membrane fuel cells. However, the synthesis of IMCs necessitates recombination of ordered Pt-M metallic bonds with high temperature driving, which is generally accompanied by side effects for catalysts' structure and performance. In this work, we highlight that semimetal atoms can trigger covalent interactions to break the synthesis-temperature limitation of platinum-based intermetallic compounds and benefit fuel-cell electrocatalysis. Attributed to partial fillings of p-block in semimetal elements, the strong covalent interaction of d-p π backbonding can benefit the recombination of ordered Pt-M metallic bonds (PtGe, PtSb and PtTe) in the synthesis process. Moreover, this covalent interaction in metallic states can further promote both electron transport and orbital fillings of active sites in fuel cells. The semimetal-Pt IMCs were obtained with a temperature 300 K lower than that needed for the synthesis of metal-Pt intermetallic compounds and reached the highest CO-tolerant oxygen reduction activity (0.794 A mg−1 at 0.9 V and 5.1% decay under CO poisoning) among reported electrocatalysts. We anticipate that semimetal-Pt IMCs will offer new insights for the rational design of advanced electrocatalysts for fuel cells. [ABSTRACT FROM AUTHOR]

Proton Exchange Membrane Fuel Cells (PEMFCs) represent a promising green solution for energy production, traditionally relying on platinum-group-metal (PGM) electrocatalysts. However, the increasing cost and limited global availability of PGMs have motivated extensive research into alternative catalyst materials. PGM-free oxygen reduction reaction (ORR) catalysts typically consist of first-row transition metal ions (Fe, Co) embedded in a nitrogen-doped carbon framework. Key factors affecting their efficacy include intrinsic activity and catalyst degradation. Thus, alternative materials with improved characteristics and the elucidation of reaction and degradation mechanisms have been the main concerns and most frequently explored research paths. High intrinsic activity and active site density can ensure efficient reaction rates, while durability towards corrosion, carbon oxidation, demetallation, and deactivation affects cell longevity. However, when moving to the actual application in PEMFCs, electrode engineering, which involves designing the catalyst layer, and other critical operational factors affecting fuel cell performance play a critical role. Electrode fabrication parameters such as ink formulation and deposition techniques are thoroughly discussed herein, explicating their impact on the electrode microstructure and formed electrochemical interface and subsequent performance. Adjusting catalyst loading, ionomer content, and porosity are part of the optimization. More specifically, porosity and hydrophobicity determine reactant transport and water removal. High catalyst loadings can enhance performance but result in thicker layers that hinder mass transport and water management. Moreover, the interaction between ionomer and catalyst affects proton conductivity and catalyst utilization. Strategies to improve the three-phase boundary through the proper ionomer amount and distribution influence catalyst utilization and water management. It is critical to find the right balance, which is influenced by the catalyst–ionomer ratio and affinity, the catalyst properties, and the layer fabrication. Overall, understanding how composition and fabrication parameters impact electrode properties and behaviour such as proton conductivity, mass transport, water management, and electrode–electrolyte interfaces is essential to maximize electrochemical performance. This review highlights the necessity for integrated approaches to unlock the full potential of PGM-free materials in PEMFC technology. Clear prospects for integrating PGM-free catalysts will drive cleaner and more cost-effective, sustainable, and commercially viable energy solutions. [ABSTRACT FROM AUTHOR]

The key factors in achieving high energy efficiency for proton exchange membrane fuel cells are reducing overpotential and increasing the oxygen reduction rate. Based on first-principles calculations, we induce H atom adsorption on 4 × 4 × 1 monolayer MoSe2 to induce spin polarization, thereby improving the catalytic performance. In the calculation of supercells, the band unfolding method is used to address the band folding effect in doped systems. Furthermore, it is evident from analyzing the unique energy band configuration of MoSe2 that a higher valley splitting value has better catalytic effects on the oxygen reduction reaction. We believe that the symmetries of the distinct adsorption site result in different overpotentials. In addition, when an even number of hydrogen atoms is adsorbed, the monolayer MoSe2 has no spin polarization. The spin can affect the electron transfer process and alter the hybrid energy with the reaction products, thereby regulating its catalytic performance. [ABSTRACT FROM AUTHOR]

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]

Polymer electrolyte membrane fuel cells (PEMFCs) have attracted much attention as highly efficient, eco-friendly energy conversion devices. However, carbon-supported Pt (Pt/C) catalysts for PEMFCs still have several problems, such as low long-term stability, to be widely commercialized in fuel cell applications. To address the stability issues of Pt/C such as the dissolution, detachment, and agglomeration of Pt nanoparticles under harsh operating conditions, we design an interesting fabrication process to produce a highly active and durable Pt catalyst by introducing a robust carbon shell on the Pt surface. Furthermore, this approach provides insights into how to regulate the carbon shell layer for fuel cell applications. Through the application of an appropriate amount of H2 gas during heat treatment, the carbon shell pores, which are integral to the structure, can be systematically modulated to facilitate oxygen adsorption for the oxygen reduction reaction. Simultaneously, the carbon shell functions as a protective barrier, preventing catalyst degradation. In this regard, we investigate an in-depth analysis of the effects of critical parameters including H2 content and the flow rate of H2/N2 mixed gas during heat treatment to prepare better catalysts. [ABSTRACT FROM AUTHOR]

Ionic liquid modification for carbon-supported platinum (Pt/C) electrocatalysts to enhance their oxygen reduction reaction (ORR) activity has been well recognized. However, the research has only been reported on the low-Pt-loading Pt/C electrocatalysts, e.g., 20 wt%, while in practical applications, usually high-Pt-loading Pt/C electrocatalysts of 45–60 wt% are used. In this work, ionic liquid modification is systematically investigated for a Pt/C electrocatalyst with 60 wt% Pt loading for its ORR activity in the cathode in proton exchange membrane fuel cells (PEMFCs). Various adsorption amounts are studied on the catalyst surface. Different modification behavior is found. Mechanism exploration shows that the adsorption of ionic liquid mainly happens on the Pt electrocatalyst surface and in the micropores of the carbon support. The highest fuel cell power performance is achieved at an ionic liquid loading of 7 wt%, which is much higher than the 3 wt% reported for the low-Pt-loading Pt/C. [ABSTRACT FROM AUTHOR]

A proton exchange membrane fuel cell (PEMFC) is an efficient and environmentally friendly power production technology that uses hydrogen energy. The cathodic oxygen reduction electrode is a critical component in the development of PEMFC. Most techniques deposit catalyst nanoparticles in areas that are inaccessible for catalytic processes, reducing platinum utilization. The substrate used in this study was carbon paper (CP) with a self-supporting structure. First, electrochemical acidification technology was employed to modify the CP's surface, followed by nanoparticle manufacturing and fixation on the CP in a single step by electrodeposition. The Pt/C0.5V2.24CP catalyst electrode demonstrated high-quality activity in the oxygen reduction reaction (ORR), with a homogeneous particle dispersion and particle size of around 50 nm. The mass activity and electrochemical active surface area (ECSA) of the Pt/C0.5V2.24CP catalyst electrode were 1.74 and 3.98 times higher than those of the Pt/C/CP-1 electrodes made with commercial catalysts, respectively. After 5000 cycles of accelerated durability testing (ADT), the mass activity and ECSA were 1.28 times and 6.16 times more than Pt/C/CP-1. This paper successfully proved the viability of electrodepositing Pt nanoparticles on CP following acidification, and that the electrochemical acidification methods have a positive influence on improving electrode ORR activity. [ABSTRACT FROM AUTHOR]

Iron‐nitrogen‐carbon (Fe‐N‐C) catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) have seriously been hindered by their poor ORR performance of Fe‐N‐C due to the low active site density (SD) and site utilization. Herein, we reported a melamine‐assisted vapor deposition approach to overcome these hindrances. The melamine not only compensates for the loss of nitrogen caused by high‐temperature pyrolysis but also effectively etches the carbon substrate, increasing the external surface area and mesoporous porosity of the carbon substrate. These can provide more useful area for subsequent vapor deposition on active sites. The prepared 0.20Mela‐FeNC catalyst shows a fourfold higher SD value and site utilization than the FeNC without the treatment of melamine. As a result, 0.20Mela‐FeNC catalyst exhibits a high ORR activity with a half‐wave potential (E1/2) of 0.861 V and 12‐fold higher ORR mass activity than the FeNC in acidic media. As the cathode in a H2‐O2 PEMFCs, 0.20Mela‐FeNC catalyst demonstrates a high peak power density of 1.30 W cm−2, outstripping most of the reported Fe‐N‐C catalysts. The developed melamine‐assisted vapor deposition approach for boosting the SD and utilization of Fe‐N‐C catalysts offers a new insight into high‐performance ORR electrocatalysts. [ABSTRACT FROM AUTHOR]

The synthesis of efficient and stable Pt alloy catalysts is a major challenge for the commercialization of PEMFC. Herein, we report a PtCo/C(N) electrocatalyst prepared by Na2CO3‐assisted urea liquid‐phase deposition strategy as an efficient cathodic oxygen reduction reaction electrocatalyst, and test its activity and stability in a rotating disc electrode and a single‐cell. The membrane electrode prepared with PtCo/C(N)‐800 °C catalyst has an output voltage of 0.652 V at 2 A/cm2 and a maximum power density of 1.501 W/cm2, which are 36 mV and 81 W/cm2 higher than those of commercial Pt/C catalyst, respectively. In addition, the mass activity and half‐wave potential of PtCo/C(N)‐800 °C are 2.44 times and 50 mV higher than those of commercial Pt/C, respectively. After 5000 voltammetric cycles, its mass activity and half‐wave potential only lose 35 A/gPt and 9 mV, respectively. XPS results show that the binding energy of Pt 4f is positively shifted relative to Pt/C‐TKK, and the d‐band center of Pt decreases, leading to weak chemical interaction between the oxygen‐containing intermediate and the surface of the electrocatalyst, which is conducive to the improvement of the ORR activity and stability of the catalyst. [ABSTRACT FROM AUTHOR]

[Display omitted] Intermetallic compounds are emerging as promising oxygen reduction reaction (ORR) catalysts for fuel cells due to their typically higher activity and durability compared to disordered alloys. However, the preparation of intermetallic catalysts often requires high-temperature annealing, which unfortunately leads to adverse sintering of the metal nanoparticles. Herein, we develop a scalable site-selective sulfur anchoring strategy that effectively suppresses alloy sintering, ensuring the formation of efficient intermetallic electrocatalysts with small sizes and high ordering degrees. The alloy-support interactions are precisely modulated by selectively modifying the alloy-support interfaces with oxidized sulfur species, thus simultaneously blocking both the nanoparticle migration and Oswald ripening pathways for sintering. Using this strategy, sub-5 nm PtCo intermetallic electrocatalysts enclosed by two atomic layers of Pt shells have been successfully prepared even at a metal loading higher than 30 wt%. The intermetallic catalysts exhibit excellent ORR performances in both rotating disk electrode and membrane electrode assembly conditions with a mass activity of 1.28 A mg Pt −1 at 0.9 V (vs. RHE) and a power density of 1.0 W cm−2 at a current density of 1.5 A cm−2. The improved performances result from the enhanced Pt-Co electronic interactions and compressive surface strain generated by the highly ordering structure, while the atomic Pt shells prevent the dissolution of Co under highly acidic conditions. This work provides new insights to inhibit the sintering of nanoalloys and would promote the scalable synthesis and applications of platinum-based intermetallic catalysts. [ABSTRACT FROM AUTHOR]

Proton exchange membrane fuel cells (PEMFCs), which have the advantages of high-power density, zero emission, and low noise, are considered ideal electrochemical conversion systems for converting hydrogen (H2) and oxygen (O2)/air into electricity. However, the oxygen reduction reaction (ORR), which is accompanied by multiple electrons, results in voltage loss and low conversion efficiency of PEMFCs. Currently, PEMFCs mainly use highload precious platinum (Pt) to promote the ORR process; however, the high cost of Pt hinders the widespread commercialization of PEMFCs. Over the past few years, metal-nitrogen-carbon single-atom catalysts (M-N-C SACs) have attracted considerable attention and have been recognized as potential Pt-based catalysts owing to their outstanding ORR activity. This review briefly introduces the components of PEMFCs. Second, we discuss the catalytic mechanisms of the M-N-C SACs for the ORR. Third, the latest advances in noble, non-noble, and heteroatom-doped M-N-C SACs used as ORR and PEMFCs cathode catalysts are systematically reviewed. In summary, we have outlined the current challenges and proposed a future perspective of M-N-C SACs for PEMFCs cathodes. [ABSTRACT FROM AUTHOR]

Nowadays, the depletion of non‐renewable energy sources has become a prominent issue, and environmental concerns such as air pollution stemming from vehicle emissions have reached a critical stage. In this manuscript, we introduce a novel approach for the fabrication of Pt/C catalysts on a large scale, utilizing a simple, rapid, and continuous pipeline microwave synthesis method. Moreover, we incorporate a heating treatment process in an N2−H2 (5 % H2) environment to enhance the activity and durability of the catalyst. The synthesized Pt/C‐400 catalyst demonstrates an impressive electrochemical active surface area of 103.2 m2/gpt and a mass‐specific activity of 315 mA/mg at a half‐wave potential of 0.9 V. Following 30000 cycles of Pt attenuation testing and 30000 cycles of carrier attenuation testing, the Pt/C‐400 catalyst exhibits a remarkable retention rate of 75 %. Furthermore, based on single‐cell testing, the Pt/C‐400 catalyst achieves a voltage of 0.606 V at a current density of 2000 mA/cm2, surpassing the performance of other Pt/C catalysts discussed in this article. This study presents an efficient and practical method for large‐scale synthesis of high‐performance and durable catalysts. The findings hold significant implications for the commercialization of Proton Exchange Membrane Fuel Cells and contribute to addressing the pressing need for sustainable energy solutions. [ABSTRACT FROM AUTHOR]

To reduce the costs of proton exchange membrane fuel cells, the amount of Pt necessary to drive efficient oxygen reduction reaction (ORR) should be minimized. Particle nanostructuring, (nano‐)alloying, and metal‐doping can yield higher activities per Pt mass through tailoring catalysts owning a high number of active sites and precise electronic properties. In this work, the atom‐precise [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4) cluster is encapsulated and activated in a zeolitic imidazolate framework (ZIF)‐8, which unlocks the access to defined, bare Pt−Co nanoclusters, Co8±xPt4±yNC@ZIF‐8, for the fabrication of highly active ORR catalysts. Upon controlled C‐interfacing and ZIF‐8‐digestion, Co‐doped Pt NPs (Pt27Co1) with a homogenous and narrow size distribution of (1.1±0.4) nm are produced on Vulcan® carbon. Restructuring of the Pt27Co1/C catalyst throughout the ORR measurement was monitored via high‐angle annular dark field‐scanning transmission electron microscopy and X‐ray photoelectron spectroscopy. The measured ORR mass activity of (0.42±0.07) A mgPt−1 and the specific activity of (0.67±0.06) mA cmECSA−2 compare favourably with the catalyst obtained by direct C‐interfacing the pristine Co8Pt4 cluster and with state‐of‐the‐art Pt/C reference catalysts. Our results demonstrate the potential of ZIF‐8‐mediated Pt−Co NP synthesis toward devising ORR catalysts with high Pt‐mass activity. [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]

This article provides an insightful understanding of how the surface property of N, S-co doped graphene can be modulated by the encapsulated Co 8 FeS 8 , resulting in easier OH desorption on the doped graphene surface for efficient alkaline oxygen reduction reaction. Particularly, the constructed interface for N, S-co doped graphene encapsulating Co 8 FeS 8 could evidently raise the catalytic activity through slightly positively-charged C active site, thus simultaneously enhancing electronic conductivity. [Display omitted] • An encapsulated catalyst of Co 8 FeS 8 @NSG has been successfully synthesized. • Surface property of the doped graphene can be modulated by Co 8 FeS 8. • The Co 8 FeS 8 @NSG exhibited superior catalytic activity for oxygen reduction electrocatalysis. • Greatly promoted electron transfer was achieved from the cobalt-rich sulfides to the doped graphene. • The enhanced performance was further unveiled by density functional theory calculations. Similar to proton exchange membrane fuel cell, anion-exchange membrane fuel cell is also a significant energy conversion device for achieving the utilization of clean hydrogen energy. However, the cathodic alkaline oxygen reduction reaction (ORR) is kinetically not favored and usually requires platinum-group metal (PGM) catalysts such as Pt/C to reduce the overpotential. The major challenge in using PGM-free catalysts for ORR is their low efficiency and poor stability, which urgently demands new concepts and strategies to address this issue. Herein, we controllably manufactured a N, S-co doped graphene encapsulating uniform cobalt-rich sulfides (Co 8 FeS 8 @NSG) by a universal synthesis strategy. After encapsulation, electron transfer from the encapsulated cobalt-rich sulfides to the doped graphene was greatly promoted, which effectively optimizes the electronic structure of the doped graphene, thereby enhancing the ORR activity of the doped graphene surface. Consequently, the Co 8 FeS 8 @NSG exhibits enhanced ORR activity with a higher half-wave potential of 0.868 V (versus reversible hydrogen electrode, vs. RHE) when compared with pure NSG (0.765 V vs. RHE). Density functional theory calculations further confirm that the construction of interface for NSG encapsulating cobalt-rich sulfides could conspicuously elevate the ORR activity through slightly positively-charged C active site and thus simultaneously enhancing electronic conductivity. [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]

Traditional synthesis methods of platinum‐rare earth metal (Pt‐RE) alloys usually involve harsh conditions and high energy consumption because of the low standard reduction potentials and high oxophilicity of RE metals. In this work, a one‐step strategy is developed by rapid Joule thermal‐shock (RJTS) to synthesize Pt‐RE alloys within tens of seconds. The method can not only realize the regulation of alloy size, but also a universal method for the preparation of a family of Pt‐RE alloys (RE = Ce, La, Gd, Sm, Tb, Y). In addition, the energy consumption of the Pt‐RE alloy preparation is only 0.052 kW h, which is 2–3 orders of magnitude lower than other reported methods. This method allows individual Pt‐RE alloy to be embedded in the carbon substrate, endowing the alloy catalyst excellent durability for oxygen reduction reaction (ORR). The performance of alloy catalyst shows negligible decay after 20k accelerated durability testing (ADT) cycles. This strategy offers a new route to synthesize noble/non‐noble metal alloys with diversified applications besides ORR. [ABSTRACT FROM AUTHOR]

Studying the ORR activity of platinum-based electrocatalysts is an urgent task in the development of materials for proton-exchange membrane fuel cells. The catalytic ink composition and the formation technique of a thin layer at the RDE play a significant role in studying ORR activity. The use of a polymer ionomer in the catalytic ink provides viscosity as well as proton conductivity. Nafion is widely used as an ionomer for research both at the RDE and in the MEA. The search for ionomers is a priority task in the development of the MEA components to replace Nafion. The study also considers the possibility of using the LF4-SK polymer as an alternative ionomer. The comparative results on the composition and techniques of applying the catalytic layer using LF4-SK and Nafion ionomers are presented, and the influence of the catalytic ink composition on the electrochemical characteristics of commercial platinum–carbon catalysts and a highly efficient platinum catalyst based on an N-doped carbon support is assessed. [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]

[Display omitted] • Single-atom Co catalysts with more Co-N 4 sites were successfully synthesized. • The catalyst exhibits an excellent ORR electrocatalytic activity. • The catalyst based Zn-air batteries shows higher peak power density. • DFT confirm that more Co-N 4 sites can lower the reaction energy barrier of ORR. Transition metal single atom catalysts (TM SACs) are the most promising oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) and metal-air batteries. However, the low density of M-N x active sites seriously hinders further improvement of the ORR electrocatalytic activity. Here, a strategy for encapsulating nitrogen-rich guest molecules (triethylenediamine cobalt complex, [Co(en) 3 ]3+) was proposed to construct a high-performance cobalt single-atom catalyst (Co-encapsulated SAC/NC). With this strategy, the guest molecules are encapsulated into metal–organic framework (MOF) cages as an additional cobalt source to boost cobalt loading, while abundant nitrogen from guest molecules contributes to the formation of Co-N 4 active sites. Remarkably, the resulting Co-encapsulated SAC/NC has a high cobalt loading amount of 4.03 wt%, and spherical aberration-corrected transmission electron microscopy (AC-TEM) has confirmed that most cobalt exists in a single-atom state. As a result, the Co-encapsulated SAC/NC exhibits excellent ORR catalytic performance with a half-wave potential of 0.88 V. Furthermore, Zn-air batteries employing Co-encapsulated SAC/NC as air cathode show high peak power density and excellent cycling stability. Density functional theory (DFT) calculations reveal that adjacent active sites have different rate-determining steps and lower reaction energy barriers than a single active site. [ABSTRACT FROM AUTHOR]

[Display omitted] Platinum-based alloy nanowire catalysts demonstrates great promise as electrocatalysts to facilitate the cathodic oxygen reduction reaction (ORR) of proton exchange membrane fuel cells (PEMFCs). However, it is still challenge to further improve the Pt atom utilization of Pt based nanowires featuring inherent structural stability. Herein, a new structure of PtCo nanowire with nanodendrites was developed using CO-assistance solvent thermal method. The dendrite structure with an average length of about 7 nm are characterized by a Pt-rich surface and the high-index facets of {5 3 3}, {3 3 1} and {3 1 1}, and grows from the ultra-fine wire structure with an average diameter of about 3 nm. PtCo nanowires with nanodendrites developed in this work shows outstanding performance for ORR, in which its mass activity of 1.036 A/mg Pt is 5.76 times, 1.74 times higher than that of commercial Pt/C (0.180 A/mg Pt) and PtCo nanowires without nanodendrites (0.595 A/mg Pt), and its mass activity loss is only 18% under the accelerated durability tests (ADTs) for 5k cycles. The significant improvement is attributed to high exposure of active sites induced by the dendrite structure with Pt-rich surface with the high-index facets and Pt-rich surface. This structure may provide a new idea for developing novel 1D Pt based electrocatalysts. [ABSTRACT FROM AUTHOR]

Over the past decades, the design of active catalysts has been the subject of intense research efforts. However, there has been significantly less deliberate emphasis on rationally designing a catalyst system with a prolonged stability. A major obstacle comes from the ambiguity behind how catalyst degrades. Several degradation mechanisms are proposed in literature, but with a lack of systematic studies, the causal relations between degradation and those proposed mechanisms remain ambiguous. Here, a systematic study of a catalyst system comprising of small particles and single atoms of Pt sandwiched between graphene layers, GR/Pt/GR, is studied to unravel the degradation mechanism of the studied electrocatalyst for oxygen reduction reaction(ORR). Catalyst suffers from atomic dissolution under ORR harsh acidic and oxidizing operation voltages. Single atoms trapped in point defects within the top graphene layer on their way hopping through toward the surface of GR/Pt/GR architecture. Trapping mechanism renders individual Pt atoms as single atom catalyst sites catalyzing ORR for thousands of cycles before washed away in the electrolyte. The GR/Pt/GR catalysts also compare favorably to state‐of‐the‐art commercial Pt/C catalysts and demonstrates a rational design of a hybrid nanoarchitecture with a prolonged stability for thousands of operation cycles. [ABSTRACT FROM AUTHOR]

[Display omitted] • A two stage confinement strategy assisted facile synthesis of 5.3 nm highly ordered PtCoZn/NC. • PtCoZn/NC ordering and graphitization are promoted by regulating composition and calcination-time. • High intrinsic activity (2.8 mA cm-2 Pt) and slight E 1/2 loss (9 mV) in ADT were achieved by PtCoZn/NC. • It is evidenced weaker O binding and stronger Pt-Co/Zn bonding enhance activity and durability. • The ionomer-free and anti-sintering feature of carbon-walls also benefit the MEA performance. Intermetallic ordered PtCo is effective for high oxygen reduction reaction (ORR) activity and stability. However, preparing small-sized, highly ordered PtM alloys is still challenging. Herein, we report a controlled two-stage confinement strategy, in which highly ordered PtCoZn/NC nanoparticles of 5.3 nm size were prepared in a scalable process. The contradiction between the high ordering degree with the small particle size as well as the atomic migration with the space confinement was well resolved. An outstanding PEMFC performance was achieved for L1 0 -PtCoZn/NC with a high mass activity (MA) of 1.21 A/mg Pt at 0.9 V iR-free , 80.1 % MA retention after 30 k cycles in H 2 -O 2 operation, and a high mass-specific power density of 8.24 W mg-1 Pt in H 2 -Air operation with a slight loss of cell voltage@0.8 A cm−2 of 28 mV after 30 k cycles. The high performance can be ascribed to the high Pt area exposure, the enhanced Pt-Co coupling, and the prevented agglomeration in the mesoporous carbon wall. Overall, this strategy may contribute to the commercialization of fuel cells. [ABSTRACT FROM AUTHOR]

In this study, density functional theory (DFT) was used to investigate the influence of temperature on the performance of a novel Cu-nitrogen-doped graphene Cu2-N8/Gr nanocomposite as a catalyst for the oxygen reduction reaction (ORR) in fuel cell applications. Our DFT calculations, conducted using Gaussian 09w with the 3–21G/B3LYP basis set, focus on the Cu-nitrogen-doped graphene nanocomposite cathode catalyst, exploring its behavior at three distinct temperatures: 298.15 K, 353.15 K, and 393.15 K, under acidic conditions. Our analysis of formation energies indicates that the structural stability of the catalyst remains unaffected as the temperature varies within the potential range of 0–7.21 V. Notably, the stability of the ORR steps experiences a marginal decrease with increasing temperature, with the exception of the intermediate OH + H2O (*OH + H + *OH). Interestingly, the optimization reveals the absence of single OH and H2O intermediates during the reactions. Furthermore, the OH + H2O step is optimized to form the OH + H + OH intermediate, featuring the sharing of a hydrogen atom between dual OH intermediates. Free energy calculations elucidate that the catalyst supports spontaneous ORR at all temperatures. The highest recorded maximum cell potential, 0.69 V, is observed at 393.15 K, while the lowest, 0.61 V, is recorded at 353.15 K. In particular, the Cu2-N8/Gr catalyst structure demonstrates a reduced favorability for the H2O2 generation at all temperatures, resulting in the formation of dual OH intermediates rather than H2O2. In conclusion, at 393.15 K, Cu2-N8/Gr exhibits enhanced catalyst performance compared to 353.15 K and 298.15 K, making it a promising candidate for ORR catalysis in fuel cell applications. [ABSTRACT FROM AUTHOR]

The use of platinum-free (Pt) cathode electrocatalysts for oxygen reduction reactions (ORRs) has been significantly studied over the past decade, improving slow reaction mechanisms. For many significant energy conversion and storage technologies, including fuel cells and metal–air batteries, the ORR is a crucial process. These have motivated the development of highly active and long-lasting platinum-free electrocatalysts, which cost less than proton exchange membrane fuel cells (PEMFCs). Researchers have identified a novel, non-precious carbon-based electrocatalyst material as the most effective substitute for platinum (Pt) electrocatalysts. Rich sources, outstanding electrical conductivity, adaptable molecular structures, and environmental compatibility are just a few of its benefits. Additionally, the increased surface area and the simplicity of regulating its structure can significantly improve the electrocatalyst's reactive sites and mass transport. Other benefits include the use of heteroatoms and single or multiple metal atoms, which are capable of acting as extremely effective ORR electrocatalysts. The rapid innovations in non-precious carbon-based nanomaterials in the ORR electrocatalyst field are the main topics of this review. As a result, this review provides an overview of the basic ORR reaction and the mechanism of the active sites in non-precious carbon-based electrocatalysts. Further analysis of the development, performance, and evaluation of these systems is provided in more detail. Furthermore, the significance of doping is highlighted and discussed, which shows how researchers can enhance the properties of electrocatalysts. Finally, this review discusses the existing challenges and expectations for the development of highly efficient and inexpensive electrocatalysts that are linked to crucial technologies in this expanding field. [ABSTRACT FROM AUTHOR]

Developing durable oxygen reduction reaction (ORR) electrocatalysts is essential to step up the large-scale applications of proton exchange membrane fuel cells (PEMFCs). Traditional ORR electrocatalysts provide satisfactory activity, yet their poor durability limits the long-term applications of PEMFCs. Porous carbon used as catalyst support in Pt/C is vulnerable to oxidation under high potential conditions, leading to Pt nanoparticle dissolution and carbon corrosion. Thus, integrating Pt nanoparticles into highly graphitic mesoporous carbons could provide long-term stability. This Perspective seeks to reframe the existing approaches to employing Pt alloys and mesoporous carbon-integrated ORR electrocatalysts to improve the activity and stability of PEMFCs. The unusual porous structure of mesoporous carbons promotes oxygen transport, and graphitization provides balanced stability. Furthermore, the synergistic effect between Pt alloys and heteroatom doping in mesoporous carbons not only provides a great anchoring surface for catalyst nanoparticles but also improves the intrinsic activity. Furthermore, the addition of Pt alloys into mesoporous carbon optimizes the available surface area and creates an effective electron transfer channel, reducing the mass transport resistance. The long-term goals for fuel-cell-powered cars, especially those designed for heavy-duty use, are well aligned with the results shown when this hybrid material is used in PEMFCs to improve performance and durability. [ABSTRACT FROM AUTHOR]

Transition metal supported N-doped carbon (M-N-C) catalysts for oxygen reduction reaction (ORR) are viewed as the promising candidate to replace Pt-group metal (PGM) for proton exchange membrane fuel cells (PEMFCs). However, the stability of M-N-C is extremely challenging due to the demetalation, H2O2 attack, etc. in the strongly oxidative conditions of PEMFCs. In this study, we demonstrate the universal effect of Zn on promoting the stability of atomically dispersed M-Nx/C (M = Co, Fe, Mn) catalysts and the enhancement mechanism is unveiled for the first time. The best-performing dual-metal-site Zn-Co-N-C catalyst exhibits a high half-wave potential (E1/2) value of 0.81 V vs. reversible hydrogen electrode (RHE) in acid and outstanding durability with no activity decay after 15,000 accelerated degradation test (ADT) cycles at 60 °C, surpassing most reported Co-based PGM-free catalysts in acid media. For comparison, the Co-N-C in the absence of Zn suffers from a rapid degradation after ADT due to the demetalation and higher H2O2 yield. X-ray adsorption spectroscopy (XAS) and density functional theory (DFT) calculations suggest the more negative formation energy (by 1.2 eV) and increased charge transfer of Zn-Co dual-site structure compared to Co-N-C could strength the Co-N bonds against the demetalation and the optimized d-band center accounts for the improved ORR kinetics. [ABSTRACT FROM AUTHOR]

Hydrogen fuel cell technology is gaining significant attention as a promising alternative for decarbonizing automotive vehicles. At the heart of hydrogen fuel cell technology is the electrode, composed of catalysts, supports, binders, and pores, which facilitates the half‐cell reactions and often governs the efficiency of fuel cells. Over the last decade, scientists have made great strides in discovering catalyst, support, and binder materials featuring unique nanostructures and compositions that significantly enhance the efficiency of those devices. While innovations must continue, we must not overlook how these materials are put together to form an electrode and how it impacts the overall efficiency. This perspective article discusses the urgent need for developing alternative electrodes for designing next generation hydrogen fuel cells. [ABSTRACT FROM AUTHOR]

[Display omitted] • A plasma-assisted approach is developed to improve the SD and site utilization of Fe N C catalyst. • The plasma-assisted approach can give a 2.81-fold SD improvement and 1.98-fold higher site utilization, simultaneously. • The carbon defects near the Fe-N 4 sites can regulate the electronic structure and promoted the intrinsic activity of Fe-N 4 sites. • The hierarchical pore structure increased the abundance of edge sites and enhance the mass transport performance of Fe N C. Enhancing the density and utilization of FeN 4 sites can serve as a viable approach to enhance the catalytic efficacy of iron nitrogen carbon (Fe N C) catalysts for oxygen reduction reaction (ORR). Herein, we present a plasma-assisted method for enhancing the porosity of nitrogen-doped carbon. Our findings indicate that the ideal ratio of mesopore to micropore area is 0.463. This ratio not only promotes the diffusion of Fe3+ but also creates additional active sites for Fe3+ loading, leading to an increase in the number of available FeN 4 sites in Fe N C electrocatalysts during pyrolysis. The density (76.5 μmol g−1) and utilization (21.08 %) of d -FeNC-30 are significantly higher than those of FeNC without plasma treatment, with a 2.8-fold and 2-fold increase, respectively. Remarkably, it displays outstanding performance, evidenced by a half-wave potential of 0.835 V (vs. RHE) in a 0.1 M HClO 4 solution and a power density of 0.860 W cm−2 in proton exchange membrane fuel cells (PEMFCs). The developed plasma-assisted approach for improving the site density (SD) and utilization of FeN 4 provides a new perspective for high-performance ORR Fe N C catalysts. [ABSTRACT FROM AUTHOR]

Membrane electrode assembly (MEA) is an essential component that mainly determines the performance of proton exchange membrane fuel cells (PEMFCs). In the electrodes of the MEA, ionomers are mixed with Pt-based nanoparticles to transfer protons to the Pt surface where electrochemical reactions take place. However, Pt catalysts suffer from the poisoning effect of ionomers with proton-conducting groups such as sulfonic acid (SA), resulting in performance deterioration. In particular, for emerging hydrocarbon-based ionomers, the benzene group, which is commonly used to improve their chemical structure, accelerates the poisoning effect. Herein, we experimentally simulate the adsorption of SA and benzenesulfonic acid (BSA) on Pt nanoparticles, revealing the orientation-dependent poisoning effect of BSA on the Pt surface.

Oxygen reduction reaction （ORR） is an important cathode reaction for metal-air batteries and proton exchange membrane fuel cells （PEMFCs）. It is of great significance to study non-noble metal catalysts with high activity and stability. In this paper， MIL-101（- Al-Fe） with hierarchical porous structure is innovatively used as the metal precursor template， and Fe-N-C catalysts with rich mesoporous structure are successfully prepared. Electrochemical test results show that Fe-N-C-MIL-900 shows the best ORR activity with half-wave potential of 0. 905 V in 0. 1 mol/L KOH electrolyte. The ORR electron transfer number of Fe-N-C-MIL-900 catalyst is 3. 98， and the H2O2 yield is less than 3%， demonstrating an obvious 4-electron ORR pathway. This work provides a new way to prepare hierarchically porous Fe-N-C catalysts with high ORR activity. [ABSTRACT FROM AUTHOR]

With the increasing demand for green and efficient energy storage devices， advanced technologies for clean energy conversion have attracted close attention from researchers. Fuel cells with environmental friendliness and high energy conversion efficiency are promising alternatives to traditional energy sources. However， Pt catalysts with high commercialization degrees in the industrial catalysis field have some problems， such as high cost， poor stability and weak anti-toxicity ability， which limits the further development of fuel cells. The development of non-Pt oxygen reduction reaction （ORR） catalysts with abundant reserves， low cost and excellent performance is an effective way to improve the efficiency of fuel cells. In this paper， based on the research results at home and abroad in recent years， various types of non-Pt system ORR catalysts， including non-precious metal and non-metal catalysts， are systematically introduced. The advantages， disadvantages and modification strategies of various catalysts are summarized， and challenges and prospects for the development of ORR electrocatalysts are put forward. [ABSTRACT FROM AUTHOR]

Chromium poisoning rapidly degrades the performance of solid oxide fuel cell (SOFC) cathode materials with superior oxygen reduction kinetics, such as La 0·6 Sr 0·4 Co 0·2 Fe 0·8 O 3 and La 0·6 Sr 0·4 CoO 3. Previously, LaNi 0.6 Fe 0.4 O 3 (LNF) demonstrated excellent resistance to chromium poisoning; however, it has relatively low electrocatalytic activity. Here, we investigate the effect of Zn substitution on the B-site of LNF cathode and deliver La(Ni 0·6 Fe 0.4) 1-x Zn x O 3-δ cathode materials with enhanced electrical and electrochemical properties. The ab initio first-principles calculations showed charged oxygen-vacancy defect formation energies of Zn-doped LNF (2.07 eV for La 8 Ni 5 Fe 2 Zn 1 O 24 and 1.83 eV for La 8 Ni 4 Fe 3 Zn 1 O 24) are lower than those of undoped LNF (2.92 eV for La 8 Ni 5 Fe 3 O 24). Various Zn-doped LNF materials are synthesized and tested for experimental validation of the DFT results. Electrical conductivity relaxation, temperature-programmed oxygen desorption, and electrochemical impedance spectroscopy analysis indicate enhanced oxygen reduction kinetics for LNFZ 3 (La(Ni 0·6 Fe 0.4) 0.97 Zn 0·03 O 3-δ). At 700 °C, LNFZ 3 has 25.4% less polarization resistance and 52.3% higher maximum power density of an anode-supported SOFC than LNF. Moreover, LNFZ 3 has the lowest polarization resistance compared with various studies reporting LNF cathode material. Furthermore, LNFZ 3 shows highly robust operation under accelerated chromium-poisoning conditions at 700 °C. The high performance and durability synergy makes the newly developed LNFZ 3 a promising cathode material for further commercial validation studies. [Display omitted] [ABSTRACT FROM AUTHOR]

Highly efficient and low‐cost Pt‐Co/CAB bimetallic cathode electrocatalysts were synthesized for hydrogen‐based proton exchange membrane fuel cell (PEMFC) using three different types of solvent, namely, dimethyl sulphoxide (DMSO), dimethylformamide (DMF), and ethylene glycol (EG). The physical characterization of synthesized cathode electrocatalysts Pt‐Co/CAB‐DMSO, Pt‐Co/CAB‐DMF and Pt‐Co/CAB‐EG was performed by scanning electron microscope–energy‐dispersive X‐ray (SEM–EDX), X‐ray diffraction (XRD), and transmission electron microscopy (TEM) techniques, whereas the electrochemical investigation of all three Pt‐Co/CAB electrocatalysts was performed by CV and EIS studies. The synthesized Pt‐Co/C‐EG electrocatalyst produced the highest power density of 19.61 mW/cm2 at a room temperature of 33°C. The power density increased to 26.11 mW/cm2, that is, 133%, when the cell operating temperature was raised from 33 to 70°C. The excellent performance of the Pt‐Co/CAB‐EG cathode electrode proves that it can be recommended as a commercial electrocatalyst for PEMFC cathode. In addition, the EG/EG was identified as the best solvent for the synthesis of Pt‐Co/CAB cathode electrocatalysts. [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]

[Display omitted] The oxygen reduction reaction (ORR) is important cathodic reaction running in several electrochemical energy conversion devices. It is still difficult to develop non-precious nanocatalysts for ORR that have high activity and increased durability for practical application. Herein, bimetallic FeMn(mIm)-N-C composite incorporated with Fe and Mn via an encapsulation-ligand exchange technique is prepared and established as an efficient ORR catalyst. The results reveal that FeMn(mIm)-N-C shows outstanding ORR performance with E 1/2 of 0.861 V and 0.778 V in alkaline and acid solutions, along with robust durability. Additionally, the assembled Zn-Air batteries (ZAB) and proton exchange membrane fuel cells (PEMFCs) both have exceptional power densities and show promise for long-term stability compared to 20% Pt/C. The present work provides a useful strategy for designing and synthesizing a reliable low-cost and high-efficient electrocatalysts for energy conversion and storage. [ABSTRACT FROM AUTHOR]

A Co‐based zeolitic imidazolate framework (ZIF‐67) derived catalyst with ultrafine CoPt nanoalloy particles is designed via a two‐step space confinement method, to achieve a robust oxygen reduction reaction (ORR) performance for proton exchange membrane fuel cell (PEMFC). The core–shell structure of ZIF‐67 (core) and SiO2 (shell) is carefully adjusted to inhibit the agglomeration of Co nanoparticles. In the subsequent adsorption−annealing process, the in situ formed graphene shell on the surface of Co nanoparticles further protects metal particles from coalescence, leading to the ultrafine CoPt nanoalloy (average diameter is 2.61 nm). Benefitting from the high utilization of Pt metal, the mass activity of CoPt nanoalloy catalyst reaches 681.8 mA mgPt−1 at 0.9 V versus RHE according to the rotating disk electrode test in 0.1 m HClO4 solution. The CoPt nanoalloy‐based PEMFC provides a high maximum power density of 2.22 W cm−2 (H2/O2) and 0.923 W cm−2 (H2/air). Simultaneously, it shows good stability in the long‐time dynamic test at low humidity, due to the robust CoPt@graphene core–shell nanostructure. This work provides a viable strategy for designing Pt‐based nanoalloy catalysts with ultrafine metal particles and high stability. [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]

Platinum‐based ordered alloy catalysts possess higher intrinsic activity in oxygen reduction reactions (ORR). High‐temperature annealing during ordered alloy formation frequently results in larger nanoparticles, and the strategy for obtaining ordered alloys at 600 °C is still undefined. Herein, an ordered Fe‐doped PtCo catalyst (O‐PtCoFe/C) with a size of sub‐4 nm was prepared at 600 °C derived from PtFe@CoO. CoO can generate oxygen vacancies by H2 reduction, lowering the atomic migration barrier and serving as a protective layer to inhibit nanoparticle migration. Experimental analyses showed the formation of O‐PtCoFe/C and electron‐rich Pt atoms due to Pt, Co, and Fe, which was advantageous for ORR performance. The mass activity of the prepared catalyst for ORR was 382.8 mA mgPt−1, which is 5.4 times greater than Pt/C. After 10000 potential cycles, the half‐wave potential was only negatively shifted by 10 mV. In PEMFC (proton exchange membrane fuel cells) tests, the O‐PtCoFe/C showed only 3 % decay after 3000 cycles, whereas the Pt/C showed a significant loss (18.4 %). This work provides an effective method for preparing ordered PtCo alloys for fuel cell cathode catalysts at 600 °C. [ABSTRACT FROM AUTHOR]

Abstract 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.

Ordered intermetallic Pt-M alloys are promising as next-generation low-Pt catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) due to the high ORR activity and excellent long-term stability. However, the mechanism behind the enhancement of ORR activity by ordering mostly comes from theoretical calculations, and experimental evidence is very lacking. Herein, we prepared a surface Pt-rich PtCo ordered alloy of about 3 nm in size, which exhibited high ORR catalytic activity, achieving impressive performance of 1.4 W cm−2 @ 0.6 V in H2-air fuel cell and mass activity of 0.62 A mgPt-1 @ 0.9 ViR-free in H2-O2 fuel cell. The key ORR intermediate, adsorbed *O2, was successfully detected by electrochemical in situ infrared spectroscopy. Compared with Pt and disordered PtCo, the ordered PtCo alloy has optimal adsorption interaction with *O2, accelerating the ORR kinetics.

Proton exchange membrane fuel cell (PEMFC) is one of the most promising energy conversion devices with high efficiency and zero emission. However, oxygen reduction reaction (ORR) at the cathode is still the dominant limiting factor for the practical development of PEMFC due to its sluggish kinetics and the vulnerability of ORR catalysts under harsh operating conditions. Thus, the development of high‐performance ORR catalysts is essential and requires a better understanding of the underlying ORR mechanism and the failure mechanisms of ORR catalysts with in situ characterization techniques. This review starts with the introduction of in situ techniques that have been used in the research of the ORR processes, including the principle of the techniques, the design of the in situ cells, and the application of the techniques. Then the in situ studies of the ORR mechanism as well as the failure mechanisms of ORR catalysts in terms of Pt nanoparticle degradation, Pt oxidation, and poisoning by air contaminants are elaborated. Furthermore, the development of high‐performance ORR catalysts with high activity, anti‐oxidation ability, and toxic‐resistance guided by the aforementioned mechanisms and other in situ studies are outlined. Finally, the prospects and challenges for in situ studies of ORR in the future are proposed. [ABSTRACT FROM AUTHOR]

This study explored the impact of solvent dielectric constant on the catalyst layer of proton exchange membrane fuel cell (PEMFC) cathodes during the oxygen reduction reaction. Electrochemical analyses were conducted at 25°C in 2.0 M H2SO4 on electrodes that had been prepared with the same Nafion and Pt loadings, but with various solvent dielectric constants for ink preparation of the catalyst layer. A Nafion loading of 0.5 mg cm-2 and Pt loading of 1 mg cm-2 were employed for all electrodes. The findings of the research revealed that the dielectric constant of the ink utilized for preparing the gas diffusion electrode reaction layer has an impact on the electrode's performance for the oxygen reduction reaction. This effect was evident in both the kinetics parameters linked to the oxygen reduction reaction and the physical characteristics of the electrode surface. In the preparation of the reaction layer, an optimal electrode performance result of 4.2 was achieved in relation to the dielectric constant. [ABSTRACT FROM AUTHOR]

The design of Pt-based electrocatalysts with high efficiency towards acid oxygen reduction reactions is the priority to promote the development and application of proton exchange membrane fuel cells. Considering that the Pt atoms on the surfaces of the electrocatalysts face the problems of interference of non-active species (such as OHad, OOHad, CO, etc.), high resistance of mass transfer at the liquid–solid interfaces, and easy corrosion when working in harsh acid. Researchers have modified the surfaces' local environment of the electrocatalysts by introducing surface modifiers such as silicon or carbon layers, amine molecules, and ionic liquids on the surfaces of electrocatalysts, which show significant performance improvement. In this review, we summarized the research progress of surface modified Pt-based electrocatalysts, focusing on the surface modification strategies and their mechanisms. In addition, the development prospects of surface modification strategies of Pt-based electrocatalysts and the limitations of current research are pointed out. [ABSTRACT FROM AUTHOR]

The high cost and poor reliability of cathodic electrocatalysts for the oxygen reduction reaction (ORR), which requires significant amounts of expensive and scarce platinum, obstructs the broad applications of proton exchange membrane fuel cells (PEMFCs). The principles of ORR and the reasons for the poor stability of Pt-based catalysts are reviewed. Moreover, this paper discusses and categorizes the strategies for enhancing the stability of Pt-based catalysts in fuel cells. More importantly, it highlights the recent progress of Pt-based stability toward ORR, including surface-doping, intermetallic structures, 1D/2D structures, rational design of support, etc. Finally, for atomic-level in-depth information on ORR catalysts in fuel cells, potential perspectives are suggested, such as large-scale preparation, advanced interpretation techniques, and advanced simulation. This review aims to provide valuable insights into the fundamental science and technical engineering for practical Pt-based ORR electrocatalysts in fuel cells. [ABSTRACT FROM AUTHOR]

Nitrogen-doped graphene is currently recognized as one of the most promising catalysts for the oxygen reduction reaction (ORR). It has been demonstrated to act as a metal-free electrode with good electrocatalytic activity and long-term operation stability, excellent for the ORR in proton exchange membrane fuel cells (PEMFCs). As a consequence, intensive research has been dedicated to the investigation of this catalyst through varying the methodologies for the synthesis, characterization, and technologies improvement. A simple, scalable, single-step synthesis method for nitrogen-doped graphene oxide preparation was adopted in this paper. The physical and chemical properties of various materials obtained from different precursors have been evaluated and compared, leading to the conclusion that ammonia allows for a higher resulting nitrogen concentration, due to its high vapor pressure, which facilitates the functionalization reaction of graphene oxide. Electrochemical measurements indicated that the presence of nitrogen-doped oxide can effectively enhance the electrocatalytic activity and stability for ORR, making it a viable candidate for practical application as a PEMFC cathode electrode. [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]

Due to the synergistic affect between Pt, Ni SAs and Pt-Ni alloy NPs, the prepared PtNi SA-NPS -NDC catalyst delivered a superior Pt utilization efficiency. [Display omitted] • Dual single-atoms of Pt, Ni and PtNi alloy NPs supported on N -doped carbon was successfully prepared. • The catalyst exhibited impressive ORR catalytic activity in acidic medium. • The catalyst delivered a superior Pt utilization efficiency of 0.033g Pt kW−1 as cathode in PEMFC. • The main active sites of the designed catalyst for ORR was determined through DFT calculations. Pt-Ni (1 1 1) alloy nanoparticles (NPs) and atomically dispersed Pt have been shown to be the most effective catalysts for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) as well as less expensive compared to pure Pt NPs. To meet reaction kinetic demands and minimize the Pt utilization at cathode in PEMFCs, we propose a novel electrocatalyst composed of dual single-atoms (Pt, Ni) and Pt-Ni alloy NPs dispersed on the surface of N -doped carbon (NDC); collectively, PtNi SA-NPS -NDC. The optimized PtNi SA-NPS -NDC catalyst displays excellent mass activity and durability compared to commercial Pt/C. Electrocatalytic measurements show that the PtNi SA-NPS -NDC catalyst, with a metal loading of 4.5 wt%, exhibited distinguished ORR performance (E 1/2 = 0.912 V) through a 4-electron (4e-) pathway, which is higher than that of commercial 20 wt% Pt/C (E 1/2 = 0.857 V). The DFT simulations indicate Pt-Ni alloy NPs and PtNiN 2 C 4 atomic structure are the mobile active sites for ORR catalytic activity in PtNi SA-NPS -NDC. As a cathode catalyst in PEMFC, the Pt utilization efficiency in the PtNi SA-NPS -NDC catalyst is 0.033 g Pt kW−1, which is 5.6 times higher than that of commercial Pt/C (0.185g Pt kW−1). Therefore, the consumption of precious metals is effectively minimized. [ABSTRACT FROM AUTHOR]

Sluggish oxygen reduction reaction (ORR) of electrodes is one of the main challenges in fuel cell systems. This study explored the kinetics of the ORR reaction mechanism, which enables us to understand clearly the electrochemical activity of the electrode. In this research, electrocatalysts were synthesized from platinum (Pt) catalyst with multi-walled carbon nanotubes (MWCNTs) coated by three polymers (polybenzimidazole (PBI), sulfonated tetrafluoroethylene (Nafion), and polytetrafluoroethylene (PTFE)) as the supporting materials by the polyol method while hexachloroplatinic acid (H2PtCl6) was used as a catalyst precursor. The oxygen reduction current of the synthesized electrocatalysts increased that endorsed by linear sweep voltammetry (LSV) curves while increasing the rotation rates of the disk electrode. Additionally, MWCNT-PBI-Pt was attributed to the maximum oxygen reduction current densities at −1.45 mA/cm2 while the minimum oxygen reduction current densities of MWCNT-Pt were obtained at −0.96 mAcm2. However, the ring current densities increased steadily from potential 0.6 V to 0.0 V due to their encounter with the hydrogen peroxide species generated by the oxygen reduction reactions. The kinetic limiting current densities (JK) increased gradually with the applied potential from 1.0 V to 0.0 V. It recommends that the ORR consists of a single step that refers to the first-order reaction. In addition, modified MWCNT-supported Pt electrocatalysts exhibited high electrochemically active surface areas (ECSA) at 24.31 m2/g of MWCNT-PBI-Pt, 22.48 m2/g of MWCNT-Nafion-Pt, and 20.85 m2/g of MWCNT-PTFE-Pt, compared to pristine MWCNT-Pt (17.66 m2/g). Therefore, it can be concluded that the additional ionomer phase conducting the ionic species to oxygen reduction in the catalyst layer could be favorable for the ORR reaction. [ABSTRACT FROM AUTHOR]