Oxygen Reduction Reaction Activity Of Catalysts Research Articles

Tailoring Oxygen Reduction Reaction on M-N-C Catalysts via Axial Coordination Engineering.

The development of fuel cells and metal-air batteries is an important link in realizing a sustainable energy supply and a green environment for the future. Oxygen reduction reaction (ORR) is the core reaction of such energy conversion devices. M-N-C catalysts exhibit encouraging ORR catalytic activity and are the most promising candidates for replacing Pt/C. The electrocatalytic performance of M-N-C catalysts is intimately related to the specific metal species and the coordination environment of the central metal atom. Axial coordination engineering presents an avenue for the development of highly active ORR catalysts and has seen considerable progress over the past decade. Nevertheless, the accurate control over the coordination environment and electronic structure of M-N-C catalysts at the atomic scale poses a big challenge. Herein, the diverse axial ligands, characterization techniques, and modulation mechanisms for axial coordination engineering are encompassed and discussed. Furthermore, some pressing matters to be solved and challenges that deserve to be explored and investigated in the future for axial coordination engineering are proposed.

ZIF-8-derived carbon substrates embedded with atomically dispersed FeN2O2 active sites as bifunctional catalysts for electrochemical carbon dioxide and oxygen reduction

Transition metal assemblies on nitrogen-containing carbon substrates have promising applications as bifunctional electrocatalysts for electrochemical carbon dioxide reduction reaction (CO2RR) and oxygen reduction reaction (ORR). In this study, ZIF-8 with a rhombic dodecahedral morphology was grown from zinc nitrate and 2-methylimidazole feedstock. Then, a nitrogen-containing carbon substrate with a pore structure was formed after the release of Zn through high-temperature calcination. During the calcination process at 700°C, Fe atoms were physically adsorbed on the nitrogen-containing carbon substrate and ligated with N/O to form FeN2O2 reactive sites. For CO2RR, FeN2O2/NC exhibited excellent catalytic properties for converting CO2 to CO, achieving a high Faraday efficiency of 95.5 % at −0.7 V. Under alkaline conditions, it demonstrated ORR performance (E1/2 = 0.83 V) comparable with that of Pt/C (E1/2 = 0.82 V). This study not only presents an energy-efficient method for CO2RR but also provides new insights into highly active catalysts for ORR.

Boosting oxygen reduction performance by copper-iron co-doped on ZIF-derived N-doped carbon nanotubes

Developing high-efficiency non-noble metal catalysts for the oxygen reduction reaction (ORR) is paramount for sustainable energy conversion. In this study, we proposed a Cu, Fe co-doped zeolite imidazole framework (ZIF)-derived nitrogen-doped carbon nanotubes catalyst (Cu–Fe@CNTs/NC) obtained by hydrothermal method and pyrolysis. The electrochemical results showed that Cu–Fe@CNTs/NC exhibited favorable oxygen reduction performance and good stability under alkaline electrolyte. The incorporation of Cu and Fe bimetallic dopants promoted the carbon nanotubes growth on ZIF nanosheets, and the collaborative action of Cu and Fe enhanced its ORR catalytic activity. These findings provide an innovative way to prepare high active non-platinum ORR catalysts.

Preparation of ultrathin sputtered gold films on palladium as efficient oxygen reduction electro-catalysts

Herein, we present the preparation of ultrathin gold (Au) films on different M (M = Pd, Pt, Rh, Ir, and Ru) electrodes (Au/M) using magnetron sputtering deposition for oxygen reduction reaction (ORR). The ORR electro-catalytic activities of prepared Au/M catalysts increase as follows: Au/Ru < Au/Ir < Au/Rh < Au/Pt < Au/Pd. Accordingly, the oxygen reduction catalytic behaviors of the Au-modified palladium (Au/Pd) thin films with various Au thicknesses (0.16, 0.24, 0.5, and 1 nm) are investigated in acidic environments. It is found that Au modifications can promote oxygen reduction performances due to the development of more catalytic active sites on the Pd catalyst through the existence of Au atoms. Noticeably, Au/Pd samples exhibit a connection in oxygen reduction ability as a function of Au thickness, with the ultrathin 0.16 nm Au/Pd being the most active ORR catalyst. Significantly, the 0.16 nm Au/Pd material demonstrates superior stability after 1000 potential cycles compared with the 0.16 nm Pt/Pd owing to the influence of Au coating and structurally stable surfaces. Therefore, surface modification with the deposition of Au films on Pd represents a favorable technique to boost both the ORR capability and stability of the electro-catalysts.

Controlled Catalyst Layer Architectures for Fuel Cell Applications

The catalyst layer composition and architecture play a pivotal role in bridging the gaps between ex situ and in situ catalyst activities in fuel cells.1 The catalyst-support architecture strongly influences the catalyst distribution, ionomer distribution and mass transport losses, occurring at high current density.2 Herein, a novel architecture based on self-standing fiber-network has been fabricated and characterized.3 The resulting porous structure of such catalyst layer is expected to control mass transport limitation across both the interface of catalyst layer by increasing the number of Triple Phase Boundaries. Further platinum catalyst is deposited onto this fibrous support as well as the ionomer. The full electrode is characterized for its morphology and electrochemically verified in both ex situ as well as in situ configurations. References (1) Jiantao Fan, Ming Chen, Zhiliang Zhao, Zhen Zhang, Siyu Ye, Shaoyi Xu, Haijiang Wang & Hui Li, “Bridging the Gap between Highly Active Oxygen Reduction Reaction Catalysts and Effective Catalyst Layers for Proton Exchange Membrane Fuel Cells”, Nature Energy, 6, 475–486, (2021).(2) Nagappan Ramaswamy, Wenbin Gu, Joseph M. Ziegelbauer and Swami Kumaraguru, “Carbon Support Microstructure Impact on High Current Density Transport Resistances in PEMFC Cathode”, Journal of The Electrochemical Society ,167, 064515, 2020.(3) Giorgio Ercolano, Filippo Farina, Sara Cavaliere, Deborah J. Jones and Jacques Rozière, “Towards Ultrathin Pt Films on Nanofibers by Surface-Limited Electrodeposition for Electrocatalytic Applications”, Journal of Materials Chemistry A , 5, 3974–3980, 2017.

Designing Highly Efficient Electrocatalyst for ORR and OER Based on Nb2CO2 MXene: The Role of Transition Metals and N-Doping Content.

Finding efficient and stable electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is imperative for advancing zinc-air batteries. Herein, the effect of transition metal anchored on Nb2CO2 with different N content to form TM-Nx-Nb2CO2 on the catalytic activity of ORR and OER is investigated by density functional theory. Among all the designed TM-Nx-Nb2CO2, Pt-N12.50%-Nb2CO2, Pt-N37.50%-Nb2CO2, Pt-N50.00%-Nb2CO2, Pd-N68.75%-Nb2CO2, and Pd-N100%-Nb2CO2 are excellent ORR electrocatalysts with ηORR values of 0.38, 0.36, 0.38, 0.38, and 0.34 V, respectively. Rh-Nb2CO2, Rh-N12.50%-Nb2CO2, Rh-N31.25%-Nb2CO2, Rh-N37.50%-Nb2CO2, Rh-N50.00%-Nb2CO2, Pt-N50.00%-Nb2CO2, Rh-N68.75%-Nb2CO2, and Rh-N81.25%-Nb2CO2 are excellent OER electrocatalysts with ηOER values of 0.33, 0.37, 0.34, 0.36, 0.37, 0.34, 0.38, and 0.33 V, respectively. Notably, Rh-Nb2CO2 and Pt-N50.00%-Nb2CO2 exhibit outstanding ORR and OER bifunctional catalytic activity with potential gap values of 0.80 and 0.72 V, respectively, which are higher than the activities of most reported bifunctional catalysts. Furthermore, electronic structure analysis indicates that the moderate adsorption strength of oxygen-containing intermediates on active centers is crucial for achieving highly active bifunctional catalysts for ORR and OER. This study provides a strategy for the design of novel ORR and OER catalysts using 2D MXene materials.

Practice of Ecological Aesthetics in Green Production of Bimetallic Carbide Catalyst for Oxygen Reduction Reaction: Integrating Technological Development with Ecological Protection

This work summarizes the disciplinary connotation of ecological aesthetics, discusses the social and philosophical background of the origination of ecological aesthetics, and applies ecological aesthetics to the research on the production processes of catalytic materials. It is found that compared with conventional chemical processes, catalytic materials synthesized using green chemical processes that conform to ecological aesthetics have advantages in raw material cost, energy consumption, environmental protection, operational complexity, and product performance. Based on this, it is proposed that, as green chemical processes develop to a certain extent, they will unify anthropocentrism and ecocentrism, and meet both human needs and ecological protection requirements. The mentioned green chemical processes adopt biomass lotus leaf stems as a carbon source to produce non-noble metal bimetallic carbide (C19Cr7Mo24)-based catalysts for oxygen reduction reaction (ORR). Its initial half-wave potential (E1/2) for catalyzing ORR in an alkaline medium is 0.903 V, the E1/2 retention rate after 50,000 cycles is 98.9%, and its peak power density in H2/O2 fuel cell reaches 1.47 W cm−2, making it one of the most active non-noble metal catalysts for ORR reported so far; its stability is unparalleled.

Engineering ORR Electrocatalysts from Co8Pt4 Carbonyl Clusters via ZIF‐8 Templating

AbstractTo 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.

Manipulation of Electronic States of Pt Sites via d-Band Center Tuning for Enhanced Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells.

Expediting the torpid kinetics of the oxygen reduction reaction (ORR) at the cathode with minimal amounts of Pt under acidic conditions plays a significant role in the development of proton exchange membrane fuel cells (PEMFCs). Herein, a novel Pt-N-C system consisting of Pt single atoms and nanoparticles anchored onto the defective carbon nanofibers is proposed as a highly active ORR catalyst (denoted as Pt-N-C). Detailed characterizations together with theoretical simulations illustrate that the strong coupling effect between different Pt sites can enrich the electron density of Pt sites, modify the d-band electronic environments, and optimize the oxygen intermediate adsorption energies, ultimately leading to significantly enhanced ORR performance. Specifically, the as-designed Pt-N-C demonstrates exceptional ORR properties with a high half-wave potential of 0.84 V. Moreover, the mass activity of Pt-N-C reaches 193.8 mA gPt-1 at 0.9 V versus RHE, which is 8-fold greater than that of Pt/C, highlighting the enormously improved electrochemical properties. More impressively, when integrated into a membrane electrode assembly as cathode in an air-fed PEMFC, Pt-N-C achieved a higher maximum power density (655.1 mW cm-2) as compared to Pt/C-based batteries (376.25 mW cm-2), hinting at the practical application of Pt-N-C in PEMFCs.

Densely accessible single atom Fe sites dispersed on porous carbon as highly stable and active ORR catalyst for PEMFC

Single-atom Fe–N–C catalysts have received ever-growing interest in proton exchange membrane fuel cells (PEMFCs) application for their utmost atomic utilization in oxygen reduction reaction (ORR). However, developing atomically dispersed Fe–N–C catalysts with both satisfactory activity and excellent stability presents great challenges. Herein, a template-activator combined strategy is developed to construct ORR catalysts with densely accessible single-atom Fe sites dispersed on hierarchically porous carbon networks. The optimized catalyst exhibits excellent oxygen reduction activity with a half-wave potential of 0.84 V and surprising stability with 93.6% retention of the initial current density after 24 hours of chronoamperometric test in acidic media. Notably, when assembled in a H2–O2 fuel cell, it shows remarkable long-term durability with only 16% loss in current density during the first 10 hours.

Bimetallic niobium-iron oxynitride as a highly active catalyst towards the oxygen reduction reaction in acidic media

Developing cost-effective acidic oxygen reduction reaction (ORR) catalysts with high performance is of great significance for proton exchange membrane fuel cells (PEMFCs) but very challenging. Transition-metal oxynitrides have high tolerance to harsh acidic media due to their excellent corrosion resistance, but they suffer from low acidic ORR activity. Here we report the discovery of a carbon-supported bimetallic niobium-iron oxynitride as a highly active and robust ORR catalyst in acidic media. This catalyst shows much higher ORR activity than its monometallic niobium oxynitride counterpart and exhibits a record high ORR activity among transition-metal oxynitrides, with an optimal ORR half-wave potential of 0.75 V vs. RHE, approaching those of atomically dispersed metal-N-C materials. It is revealed that the optimal catalyst has two types of Fe species with low oxidation state and two additional oxygen adsorption sites with high reactivity in comparison to its monometallic niobium oxynitride counterpart, therefore resulting in its remarkable ORR activity. Our work provides a new direction to explore efficient acidic ORR catalysts with low costs.

Self‐Assembled Perovskite Nanocomposite With Beneficial Lattice Tensile Strain as High Active and Durable Cathode for Low Temperature Solid Oxide Fuel Cell

AbstractThe sluggish kinetics of oxygen reduction reaction (ORR) at low temperatures and the fast degradation of the cathode are the main obstacles to the commercialization of solid oxide fuel cells (SOFCs). However, it is still very challenging to achieve both high catalytic activity and favorable stability for single‐phase materials. Herein, a highly active and durable nanocomposite cathode (Ba0.5Sr0.5)0.75Pr0.25Co0.575Fe0.3W0.125O3‐δ (BSPCFW) for low‐temperature SOFC (≤650 °C) is presented, which self‐assembles into two cubic perovskites: the simple perovskite Pr0.38Ba0.25Sr0.37Co0.62Fe0.38O3‐δ (PBSCF‐c) and the B‐site cations ordered double perovskite Ba1.30Sr0.70Co1.0Fe0.25W0.75O6‐δ (BSCFW‐c). The former PBSCF‐c serves as the highly conductive and active catalyst for ORR, while the latter BSCFW‐c with a large lattice parameter introduces a key beneficial lattice tensile strain into the PBSCF‐c phase through a coherent interface, which significantly promotes the ORR activity at low temperatures with the area specific resistance of 0.034 Ω cm2 at 650 °C, and the long‐term stability of 2 years storage and 1280 h operation in symmetrical cell. The introduction of the beneficial lattice tensile strain in self‐assembled composite catalysts is an effective way to synergistically enhance the electrochemical activity and durability of the electrode materials for electrochemical devices.

Enhanced Electrochemical Oxygen Reduction By Modulating Electronic Structures of Platinum Nanoparticles By Nitrogen-Introduced Carbon Support

With universal attention to sustainable development, the eco-friendly generation of energy has been emerging as one of the most important projects. Fuel cells, electrochemical energy conversion devices using hydrogen as the energy source, are one of the key solutions to this urgent problem. To get an effective energy conversion efficiency, understanding the reaction of fuel cells that occurred in each part is essential. Oxygen reduction reaction (ORR), which occurred in the cathode, is the main reason for reducing the efficiency because of its sluggish reaction kinetics. Therefore, it is necessary to develop highly active ORR catalysts to get efficient fuel cells. Among the various elements, platinum (Pt) has been known as the best active metal for its optimized binding properties with oxygen so plenty of research related to Pt-based materials has been reported so far. Most of them focused on electrocatalytic active material such as Pt-alloy nanocrystals or facet-controlled nanostructures where the electrochemical reaction occurred, while the surface state of the support has been largely neglected. Generally, carbon support for nanocrystals has been regarded as inert for reaction pathways on metal nanocrystals. In this study, we demonstrate that surface N-functionalization of carbon support can modulate electronic structures of supported Pt nanocrystals. Electronic structure-modified Pt nanocrystals show less affinity toward oxygen adsorption species, which means attenuated surface coverage and thereby much higher availability of Pt active sites during electrocatalysis. Consequently, reaction kinetics and mass activity are remarkably improved as much as Pt-M (M=Transition metals) alloy nanocrystals. This study will suggest the importance of surface engineering in carbon support as a factor in enhancing the electrocatalytic performance of nano-particulate electrocatalysts.

Design of nanosheet/nanotube composites of Fe, N-doped carbon for enhanced oxygen reduction in zinc-air batteries

Low-density active sites, low-mass transfer rate, and poor stability of carbon-based catalytic materials from the pyrolysis of conventional metal-nitrogen complexes can hamper the oxygen reduction reaction (ORR). Herein, a composite structure of nitrogen-doped carbon nanosheets grafted with carbon nanotubes are synthesized by Zn-ZIF-L breaking and co-functionalized by coupling Fe2O3 nanoparticles with active Fe-Nx species to form an active ORR catalyst (D-FeNC/MOF). Under the synergetic effect of high-density active sites and multi-size pore distribution, the diffusion resistance of oxygen in the pores can be decreased to facilitate the transfer of reactants and products, and the improvement of ORR efficiency. Comparing to the commercial Pt/C catalyst, the d-FeNC/MOF has exhibited a more positive half-wave potential of 0.875 V (vs. RHE) and a higher catalytic stability. Besides, the zinc-air battery assembled with d-FeNC/MOF as a cathode catalyst can also offer a maximum power density of 170 mW cm−2 and a specific energy density of 842 Wh kg−1. This work can provide a new way for designing non-Pt catalysts for various electrochemical energy devices.

Co-Doped Ni3V2O8 Nanofibers Achieving d-d Orbital Coupling for Electrocatalytic Oxygen Reduction.

Efficient and robust non-platinum-group metal electrocatalysts for O2 reduction are a prerequisite for practical high-performance fuel cells and metal-air batteries. Herein, we reported an integrated principle of gradient electrospinning and controllable pyrolysis to fabricate various Co-doped Ni3V2O8 nanofibers with high oxygen reduction reaction (ORR) activity. The representative Co1.3Ni1.7V2O8 nanofibers showed outstanding ORR performance in an alkaline solution with a half-wave potential (E1/2) of 0.874 V vs RHE, along with high long-term stability. Furthermore, the introduction of Co could effectively restrain the growth of nanoparticles and change the electronic structure of Ni3V2O8. Control experiments and theoretical calculations demonstrated that upon Co-doping, the hybridization between the 3d orbital for both Co and Ni guaranteed the stable adsorption interaction with O2 over Ni and Co metal centers. Meanwhile, the weakened binding ability of Ni3V2O8 to OH* reduced the ORR free energy. Overall, the synergistic effect of Co and Ni metal cations essentially reflected the origin of ORR activity on the Co-doped Ni3V2O8 nanofibers. This work offers new insights and practical guidance for designing highly active ORR catalysts for electrochemical clean energy conversion and storage.

On the Challenge of Obtaining an Accurate Solvation Energy Estimate in Simulations of Electrocatalysis

The effect of solvation on the free energy of reaction intermediates adsorbed on electrocatalyst surfaces can significantly change the thermochemical overpotential, but accurate calculations of this are challenging. Here, we present computational estimates of the solvation energy for reaction intermediates in oxygen reduction reaction (ORR) on a B-doped graphene (BG) model system where the overpotential is found to reduce by up to 0.6 V due to solvation. BG is experimentally reported to be an active ORR catalyst but recent computational estimates using state-of-the-art hybrid density functionals in the absence of solvation effects have indicated low activity. To test whether the inclusion of explicit solvation can bring the calculated activity estimates closer to the experimental reports, up to 4 layers of water molecules are included in the simulations reported here. The calculations are based on classical molecular dynamics and local minimization of energy using atomic forces evaluated from electron density functional theory. Data sets are obtained from regular and coarse-grained dynamics, as well as local minimization of structures resampled from dynamics simulations. The results differ greatly depending on the method used and the solvation energy estimates are deemed untrustworthy. It is concluded that a significantly larger number of water molecules is required to obtain converged results for the solvation energy. As the present system includes up to 139 atoms, it already strains the limits of computational feasibility, so this points to the need for a hybrid simulation approach where efficient simulations of much larger number of solvent molecules is carried out using a lower level of theory while retaining the higher level of theory for the reacting molecules as well as their near neighbors and the catalyst. The results reported here provide a word of caution to the computational catalysis community: activity predictions can be inaccurate if too few solvent molecules are included in the calculations.

Zinc-Mediated Template Synthesis of Hierarchical Porous N-Doped Carbon Electrocatalysts for Efficient Oxygen Reduction.

The development of highly active and low-cost catalysts for use in oxygen reduction reaction (ORR) is crucial to many advanced and eco-friendly energy techniques. N-doped carbons are promising ORR catalysts. However, their performance is still limited. In this work, a zinc-mediated template synthesis strategy for the development of a highly active ORR catalyst with hierarchical porous structures was presented. The optimal catalyst exhibited high ORR performance in a 0.1 M KOH solution, with a half-wave potential of 0.89 V vs. RHE. Additionally, the catalyst exhibited excellent methanol tolerance and stability. After a 20,000 s continuous operation, no obvious performance decay was observed. When used as the air-electrode catalyst in a zinc-air battery (ZAB), it delivered an outstanding discharging performance, with peak power density and specific capacity as high as 196.3 mW cm-2 and 811.5 mAh gZn-1, respectively. Its high performance and stability endow it with potential in practical and commercial applications as a highly active ORR catalyst. Additionally, it is believed that the presented strategy can be applied to the rational design and fabrication of highly active and stable ORR catalysts for use in eco-friendly and future-oriented energy techniques.

Post-Synthesis Heat Treatment of Doped PtNi-Alloy Fuel-Cell Catalyst Nanoparticles Studied by In-Situ Electron Microscopy

Octahedral-shaped PtNi-alloy nanoparticles are highly active oxygen reduction reaction catalysts for the cathode in proton exchange membrane fuel cells. However, one major drawback in their application is their limited long-term morphological and compositional stability. Here, we present a detailed in situ electron microscopy characterization of thermal annealing on octahedral-shaped PtNi catalysts as well as on doped octahedral PtNi(Mo) and PtNi(MoRh) catalysts. The evolution of their morphology and composition was quantified during both ex situ and in situ experiments using energy dispersive X-ray spectroscopy in a scanning transmission electron microscope under a hydrogen atmosphere and in vacuum. Morphological changes upon heating, i.e., a gradual loss of the octahedral shape and a continuous rounding of the particles, were observed, as well as evidence for increased alloying. Furthermore, the evolution of the shape of the PtNi(Mo) nanoparticles was quantified using in situ experiments under hydrogen atmosphere in a transmission electron microscope. The shape change of the particles was quantified using segmentation maps created by a neural network. It has been demonstrated that morphological changes crucially depend on the composition and surface doping: doping with Mo or Mo/Rh significantly stabilizes the structure, allowing for persistence of a truncated octahedral shape during heat treatments.

Enhancement Mechanism of Pt/Pd-Based Catalysts for Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) is one of the key catalytic reactions for hydrogen fuel cells, biofuel cells and metal-air cells. However, due to the complex four-electron catalytic process, the kinetics of the oxygen reduction reaction are sluggish. Platinum group metal (PGM) catalysts represented by platinum and palladium are considered to be the most active ORR catalysts. However, the price and reserves of Pt/Pd are major concerns and issues for their commercial application. Improving the catalytic performance of PGM catalysts can effectively reduce their loading and material cost in a catalytic system, and they will be more economical and practical. In this review, we introduce the kinetics and mechanisms of Pt/Pd-based catalysts for the ORR, summarize the main factors affecting the catalytic performance of PGMs, and discuss the recent progress of Pt/Pd-based catalysts. In addition, the remaining challenges and future prospects in the design and improvement of Pt/Pd-based catalysts of the ORR are also discussed.

Pt17 nanocluster electrocatalysts: preparation and origin of high oxygen reduction reaction activity.

We recently found that [Pt17(CO)12(PPh3)8]z (Pt = platinum; CO = carbon monoxide; PPh3 = triphenylphosphine; z = 1+ or 2+) is a Pt nanocluster (Pt NC) that can be synthesized with atomic precision in air. The present study demonstrates that it is possible to prepare a Pt17-supported carbon black (CB) catalyst (Pt17/CB) with 2.1 times higher oxygen reduction reaction (ORR) activity than commercial Pt nanoparticles/CB by the adsorption of [Pt17(CO)12(PPh3)8]z onto CB and subsequent calcination of the catalyst. Density functional theory calculation strongly suggests that the high ORR activity of Pt17/CB originates from the surface Pt atoms that have an electronic structure appropriate for the progress of ORR. These results are expected to provide design guidelines for the fabrication of highly active ORR catalysts using Pt NCs with a diameter of about 1 nm and thereby enabling the use of reduced amounts of Pt in polymer electrolyte fuel cells.