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Proton exchange membrane fuel cells (PEMFCs) have been considered by many countries and enterprises because of their cleanness and efficiency. However, due to their high cost and low platinum utilization rate, the commercialization process of PEMFC is severely limited. The cathode catalyst layer (CCL) plays an important role in manipulating the performance and lifespan of PEMFCs, which makes them one of the most significant research focuses in this community. In the CCL, the intrinsic activity and stability of the catalysts determine the performance and lifetime of the catalyst layer. In this paper, the composition and working principle of the PEMFC and cathode catalyst layer are briefly introduced, focusing on Pt-based catalysts for oxygen reduction reactions (ORRs). The research progress of Pt-based catalysts in the past five years is particularly reviewed, mainly concentrating on the development status of emerging Pt-based catalysts which are popular in the current research field, including novel concepts like phase regulation (intermetallic alloys and high-entropy alloys), interface engineering (coupled low-Pt/Pt-free catalysts), and single-atom catalysts. Finally, the future research and development directions of Pt-based ORR catalysts are summarized and prospected. [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]

Pt-based binary alloy catalysts with different structures have been designed to boost the catalytic activity of oxygen reduction reaction (ORR), however, the dissolution of the transition metals leads to insufficient catalyst durability. In order to solve this problem, a self-assembly Pt3Co superlattice catalyst is reported in this paper, which exhibits enhancement in both activity and durability towards ORR. Compared with commercial Pt catalyst, the mass activity and specific activity of Pt3Co superlattice are significantly improved. The Pt3Co superlattice dropped only 9.2% and 12.4% in the mass activity and specific activity after 5000 cycles of durability tests. Moreover, the mechanistic studies find that the improvement of the catalyst performance is mainly dominated by reducing the energy of oxygen adsorption to a more suitable energy, optimizing the electronic structure of d-band, and suppressing the leaching of Co. This work provides a strategy to prepare superlattice catalyst with great activity and durability toward ORR. [ABSTRACT FROM AUTHOR]

Developing a non-platinum catalyst that effectively catalyzes the oxygen reduction reaction (ORR) is highly significant for metal–air batteries. Metal and nitrogen co-doped carbons (M-N-Cs) have emerged as alternative candidates to platinum. In this work, dual-metal Pd/Fe-N-C electrocatalysts were synthesized by the one-step pyrolysis of phytic acid, melamine, and Pd/Fe-based salts. The Pd/Fe-N-C catalyst exhibited a good catalytic ability during the ORR process and outperformed the commercial Pt/C catalyst as regards mass activity, catalytic stability, and methanol tolerance. It was found that Pd-Nx is the active center, and the synergistic effect from the Fe component introduction endowed the Pd/Fe-N-C with an excellent catalytic performance towards the ORR. When assembled into a Zn–air battery, its specific capacity was ~775 mAh gZn−1. Meanwhile, the peak power density could reach 3.85 W mgPd−1, i.e., 3.4 times that of the commercial Pt/C catalyst (1.13 W mgPt−1). This implies that the Pd/Fe-N-C catalyst has potential applications in metal–air batteries. [ABSTRACT FROM AUTHOR]

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

Fe-N-doped carbon (Fe-N-C)-based electrocatalysts are considered to be promising alternatives to replace Pt-based catalysts for oxygen reduction reactions (ORR). Here, we reported a simple and effective approach to prepare Fe-N-C-based electrocatalysts with the shape of two-dimensional nanosheets (termed Fe/NCNSs) to enhance the ORR performance. Fe/NCNSs were prepared by the calcination of Fe/Zn dual-metal ZIFs nanosheets as precursors. Benefiting from its higher specific surface area, electrochemically active surface area, and proportion of pyridinic N and Fe-N, the optimized Fe/NCNS showed excellent ORR performance both in acidic (E1/2 = 0.725 V vs. RHE) and alkaline (E1/2 = 0.865 vs. RHE) media, being 23 mV more negative and 24 mV more positive than that of a commercial Pt/C. The optimized Fe/NCNS also exhibited long durability. In addition, the Zn-air battery with Fe/NCNS-1 and RuO2 as the air catalyst exhibited high power density (1590 mW cm−2 at a current density of 2250 mA cm−2) and superior charging/discharging durability. [ABSTRACT FROM AUTHOR]

This review considers the features of the catalysts with different nanoparticle structures architecture transformation under the various pre-treatment types. Based on the results of the publications analysis, it can be concluded that the chemical or electrochemical activation of bimetallic catalysts has a significant effect on their composition, microstructure, and catalytic activity in the oxygen reduction reaction. The stage of electrochemical activation is recommended for use as a mandatory catalyst pre-treatment to obtain highly active de-alloyed materials. The literature is studied, which covers possible variants of the structural modification under the influence of thermal treatment under different processing conditions. Additionally, based on the literature data analysis, recommendations are given for the thermal treatment of catalysts alloyed with various d-metals. [ABSTRACT FROM AUTHOR]

Hollow Pt-based nanoparticles are known to possess the properties of high electrocatalytic activity and durability. Nonetheless, their practical applications as catalytic materials are limited because of the requirement for exhaustive preparation. In this study, we prepared carbon-supported hollow PtNix (x = the moles of the Ni precursor to the Pt precursor in the catalyst preparation step) catalysts using a one-step preparation method, which substantially reduced the complexity of the conventional method for preparing hollow Pt-based catalysts. In particular, this hollow structure formation mechanism was proposed based on extensive characterizations. The prepared catalysts were examined to determine if they could be used as electrocatalysts for the oxygen reduction reaction (ORR). Among the investigated catalysts, the acid-treated hollow PtNi3/C catalyst demonstrated the best ORR activity, which was 3 times higher and 2.3 times higher than those of the commercial Pt/C and acid-treated particulate PtNi3/C catalysts, respectively. [ABSTRACT FROM AUTHOR]

We report here, a strategy to prepare Pt/Pd nanoparticles decorated with Co-N-C materials, where Co-N-C was obtained via pyrolysis of ZIF-67 directly. As-prepared Pt/Pd/Co-N-C catalysts showed excellent ORR performance, offered with a higher limit current density (6.6 mA cm−2) and similar half-wave potential positive (E1/2 = 0.84 V) compared with commercial Pt/C. In addition to an ORR activity, it also exhibits robust durability. The current density of Pt/Pd/Co-N-C decreased by only 9% after adding methanol, and a 10% current density loss was obtained after continuous testing at 36,000 s. [ABSTRACT FROM AUTHOR]

New highly active electrocatalysts were obtained by depositing bimetallic Pt-Cu nanoparticles on the surface of an N-doped carbon support. The structural–morphological characteristics and electrochemical behavior of the catalysts were studied. Using current stress testing protocols, their resistance to degradation was assessed in comparison with that of a commercial Pt/C material. A combined approach to catalyst synthesis that consists in alloying platinum with copper and doping the support makes it possible to obtain catalysts with a uniform distribution of bimetallic nanoparticles on the carbon surface. The obtained catalysts exhibit high activity and durability. [ABSTRACT FROM AUTHOR]

In order to fill the research gap of high metal loading of high performance PtNi alloy catalysts, a PtNi/C alloy nano-catalyst with metal loading more than 50 wt.% and core-shell like structure was prepared by ethylene glycol reduction, high temperature annealing, and acid pickling. The electrochemical test results showed that the prepared PtNi alloy catalyst had excellent electrochemical activity: the electrochemical surface area (ECSA) was 63.8 m2·gPt−1, and the mass activity (MA) was 0.574 A·mgPt−1, which is 2.73 times greater than those of the Pt/C JM (Johnson Matthey) catalyst. The durability of the PtNi/C catalyst was further investigated. After 30 K cycles of accelerated durability test, the ECSA and MA of the PtNi/C alloy catalyst decreased by 10.2% and 31.2%, respectively. The PtNi/C alloy catalyst prepared in this study has excellent catalytic activity and overcomes the problem of insufficient durability of traditional alloy catalysts and has the potential for large-scale commercial application. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) at the cathode is a fundamental process and functions a pivotal role in fuel cells and metal-air batteries. However, the electrochemical performance of these technologies has been still challenged by the high cost, scarcity, and insufficient durability of the traditional Pt-based ORR electrocatalysts. Heteroatom-doped nanocarbon electrocatalysts with competitive activity, enhanced durability, and acceptable cost, have recently attracted increasing interest and hold great promise as substitute for precious-metal catalysts (e.g., Pt and Pt-based materials). More importantly, three-dimensional (3D) porous architecture appears to be necessary for achieving high catalytic ORR activity by providing high specific surface areas with more exposed active sites and large pore volumes for efficient mass transport of reactants to the electrocatalysts. In this review, recent progress on the design, fabrication, and performance of 3D heteroatom-doped nanocarbon catalysts is summarized, aiming to elucidate the effects of heteroatom doping and 3D structure on the ORR performance of nanocarbon catalysts, thus promoting the design of highly active nanocarbon-based ORR electrocatalysts. [ABSTRACT FROM AUTHOR]

Pt/C and Pt/x-SnO2/C catalysts (where x is mass content of SnO2) were synthesized using a polyol method. Their kinetic properties towards oxygen reduction reaction were studied by a rotating disk electrode (RDE) technique in a temperature range from 1 to 50 °C. The SnO2 content of catalyst samples was 5 and 10 wt.%. A quick evaluation of the catalyst activity, electrochemical behavior and average number of transferred electrons were performed using the RDE technique. It has been shown that the use of x-SnO2 (through modification of the carbon support) in a binary system together with Pt does not reduce the catalyst activity in the temperature range of 1–30 °C. The temperature rising up to 50 °C resulted in composite catalyst activity reduction at about 30%. [ABSTRACT FROM AUTHOR]

The goal of this research was to synthesize activated nitrogen-doped nanocarbons with high specific surface area and adjustable pore size distribution using wood charcoal as a raw material. The resulting carbon materials were tested for possible application as oxygen reduction reaction catalysts in alkaline media. Activated carbons were obtained using a thermochemical activation method with NaOH. Nitrogen was introduced into activated carbons using dicyandiamide solution. It was demonstrated that the content of introduced nitrogen depends on oxygen content in the structure of the activated carbon. The oxygen reduction reaction activity of the activated and nitrogen-doped carbon material was comparable with a commercial 20% Pt/C catalyst. Electrocatalytic properties of the synthesized N-doped wood-derived carbon catalysts may be associated with the highly developed surface area, specific ratio of micro- and mesopores, as well as the high percentage of pyridinic nitrogen. [ABSTRACT FROM AUTHOR]

MOF–derived porous carbon is a type of promising catalyst to replace expensive Pt–based catalysts for oxygen reduction reaction (ORR). The catalytic activity for ORR depends closely on pyrolysis conditions. In this work, a Co–doped ZIF–8 material was chosen as a research object. The effect of pyrolysis conditions (temperature, heating rate, two–step heating) on the ORR performance of ZIF–derived carbon catalysts was systematically studied. The Co–ZIF–8 catalyst carbonized at 900 °C exhibits better ORR catalytic activity than that carbonized at 800 °C and 1000 °C. Moreover, a low heating rate can enhance catalytic activity. Two–step pyrolysis is proven to be an effective way to improve the performance of catalysts. Reducing the heating rate in the low–temperature stage is more beneficial to the ORR performance, compared to the heating rate in the high–temperature stage. The results show that the Co–ZIF–8 catalyst exhibits the best performance when the precursor was heated to 350 °C at 2 °C/min, and then heated to 900 °C at 5 °C/min. The optimum Co–ZIF–8 catalyst shows a half–wave potential of 0.82 V and a current density of 5.2 mA·cm−2 in 0.1 M KOH solution. It also exhibits high content of defects and good graphitization. TEM mapping shows that Co and N atoms are highly dispersed in the polyhedral carbon skeleton. However, two–step pyrolysis has no significant effect on the stability of the catalyst. [ABSTRACT FROM AUTHOR]

Mn-doped spinel oxides MnxNi1−xCo2O4 (x = 0, 0.3, 0.5, 0.7, and 1) were synthesized using the citric acid-assisted sol–gel method. The Mn0.5Ni0.5Co2O4 (x = 0.5) supported on carbon nanosheets, Mn0.5Ni0.5Co2O4/C, was also prepared using the same method employing NaCl and glucose as a template and carbon source, respectively, followed by pyrolysis under an inert atmosphere. The electrocatalytic oxygen reduction reaction (ORR) activity was performed in alkaline media. Cyclic voltammetry (CV) was used to investigate the oxygen reduction performance of MnxNi1−xCo2O4 (x = 0, 0.3, 0.5, 0.7, and 1), and Mn0.5Ni0.5Co2O4 was found to be the best-performing electrocatalyst. Upon supporting the Mn0.5Ni0.5Co2O4 on a carbon sheet, the electrocatalytic activity was significantly enhanced owing to its large surface area and the improved charge transfer brought about by the carbon support. Rotating disk electrode studies show that the ORR electrocatalytic activity of Mn0.5Ni0.5Co2O4/C proceeds via a four-electron pathway. Mn0.5Ni0.5Co2O4/C was found to possess E1/2(V) = 0.856, a current density of 5.54 mA cm−2, and a current loss of approximately 0.11% after 405 voltammetric scan cycles. This study suggests that the interesting electrocatalytic performance of multimetallic transition metal oxides can be further enhanced by supporting them on conductive carbon materials, which improve charge transfer and provide a more active surface area. [ABSTRACT FROM AUTHOR]

Although oxygen reduction reaction (ORR) catalysts have been extensively investigated and developed, there is a lack of clarity on catalysts that can balance high performance and low cost. Pt-based intermetallic nanocrystals are of special interest in the commercialization of proton exchange membrane fuel cells (PEMFCs) due to their excellent ORR activity and stability. This review summarizes the wide range of applications of Pt-based intermetallic nanocrystals in cathode catalysts for PEMFCs and their unique advantages in the field of ORR. Firstly, we introduce the fundamental understanding of Pt-based intermetallic nanocrystals, and highlight the difficulties and countermeasures in their synthesis. Then, the progress of theoretical and experimental studies related to the ORR activity and stability of Pt-based intermetallic nanocrystals in recent years are reviewed, especially the integrated strategies for enhancing the stability of ORR. Finally, the challenges faced by Pt-based intermetallic nanocrystals are summarized and future research directions are proposed. In addition, numerous design ideas of Pt-based intermetallic nanocrystals as ORR catalysts are summarized, aiming to promote further development of commercialization of PEMFC catalysts while fully understanding Pt-based intermetallic nanocrystals. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) have been explored as a surface modification strategy to promote the oxygen reduction reaction (ORR) on Pt/C and their chemical structures were identified to have strong influence on the ORR activities. To better understand the roles of anion and cation of ILs on the catalytic reaction, two cations ([MTBD]+ and [bmim]+) were paired with three anions ([TFSI]−, [beti]−, and [C4F9SO3]−) to form various IL structures. By systematically varying the IL combinations and studying their effects on the electrochemical behaviors, such as electrochemical surface area and specific ORR activities, it was found that cation structure had a higher influence than anion, and the impact of the [MTBD]+ series was stronger than the [bmim]+ series. In addition to the investigation in the half-cell, studies were also extended to the membrane electrode assembly (MEA). Considerable performance enhancements were demonstrated in both the kinetic region and high current density region with the aid of IL. This work suggests that IL modification can provide a complementary approach to improve the performance of proton exchange membrane fuel cells. [ABSTRACT FROM AUTHOR]

Since the reaction rate and cost for cathodic catalyst in polymer electrolyte membrane fuel cells are obstacles for commercialization, the high-performance catalyst for oxygen reduction reaction is necessary. The Ni encapsulated with N-doped graphitic carbon (Ni@NGC) prepared with ethylenediamine and carbon black is employed as an efficient support for the oxygen reduction reaction. Characterizations show that the Ni@NGC has a large surface area and mesoporous structure that is suitable to the support for the Pt catalyst. The catalyst structure is identified and the size of Pt nanoparticles distributed in the narrow range of 2–3 nm. Four different nitrogen species are doped properly into graphitic carbon structure. The Pt/Ni@NGC shows higher performance than the commercial Pt/C catalyst in an acidic electrolyte. The mass activity of the Pt/Ni@NGC in fuel cell tests exhibits over 1.5 times higher than that of commercial Pt/C catalyst. The Pt/Ni@NGC catalyst at low Pt loading exhibits 47% higher maximum power density than the Pt/C catalyst under H2-air atmosphere. These results indicate that the Ni@NGC as a support is significantly beneficial to improving activity. [ABSTRACT FROM AUTHOR]

An electrochemical nanoflowers manganese oxide (MnO2) catalyst has gained much interest due to its high stability and high specific surface area. However, there are a lack of insightful studies of electrocatalyst performance in nanoflower MnO2. This study assesses the electrocatalytic performances of nanoflower structure MnO2 for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in a zinc–air battery as a bifunctional electrocatalyst. The prepared catalyst was characterized in term of morphology, crystallinity, and total surface area. Cyclic voltammetry and linear sweep voltammetry were used to evaluate the electrochemical behaviors of the as-prepared nanoflower-like MnO2. The discharge performance test for zinc–air battery with a MnO2 catalyst was also conducted. The results show that the MnO2 prepared at dwell times of 2, 4 and 6 h were nanoflowers, nanoflower mixed with nanowires, and nanowires with corresponding specific surface areas of 52.4, 34.9 and 32.4 g/cm2, respectively. The nanoflower-like MnO2 catalyst exhibits a better electrocatalytic performance towards both ORR and OER compared to the nanowires. The number of electrons transferred for the MnO2 with nanoflower, nanoflower mixed with nanowires, and nanowire structures is 3.68, 3.31 and 3.00, respectively. The as-prepared MnO2 nanoflower-like structure exhibits the best discharge performance of 31% higher than the nanowires and reaches up to 30% of the theoretical discharge capacity of the zinc–air battery. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) is a key process for the operation of fuel cells. To accelerate the sluggish kinetics of ORR, a wide range of catalysts have been proposed and tested. In this work, a nano-dispersed copper-impregnated platinum catalyst prepared by electrodeposition of platinum on a poly[Cu(Salen)] template followed by polymer destruction is described. In addition to the high activity of the thus prepared catalyst in the oxygen reduction reaction surpassing that of both polycrystalline platinum catalyst and the commercial carbon-platinum catalyst ("E-TEK"), it showed remarkable tolerance to the presence of methanol in solution. [ABSTRACT FROM AUTHOR]

Heteroatom-doped carbon materials have been extensively studied in the field of electrochemical catalysis to solve the challenges of energy shortage. In particular, there is vigorous research activity in the design of multi-element co-doped carbon materials for the improvement of electrochemical performance. Herein, we developed a supramolecular approach to construct metallosupramolecular polymer hollow spheres, which could be used as precursors for the generation of carbon shells co-doped with B, N, F and Fe elements. The metallosupramolecular polymer hollow spheres were fabricated through a simple route based on the Kirkendall effect. The in situ reaction between the boronate polymer spheres and Fe3+ could easily control the component and shell thickness of the precursors. The as-prepared multi-element co-doped carbon shells showed excellent catalytic activity in an oxygen reduction reaction, with onset potential (Eonset) 0.91 V and half-wave (Ehalf-wave) 0.82 V vs reversible hydrogen electrode (RHE). The fluorine element in the carbon matrix was important for the improvement of oxygen reduction reaction (ORR) activity performance through designing the control experiment. This supramolecular approach may afford a new route to explore good activity and a low-cost catalyst for ORR. [ABSTRACT FROM AUTHOR]