Structural Dependence of Oxygen Reduction Reaction on Palladium Nanocrystals
01 Aug 2011-Iss: 16, pp 1011-1011
TL;DR: The ORR activity of Pd nanocubes was one order of magnitude higher than that of PD octahedra, and comparable to that of the state-of-the-art Pt catalysts.
Abstract: We have synthesized sub-10 nm Pd cubic and octahedral nanocrystals and then evaluated their activities towards oxygen reduction reaction (ORR). The ORR activity of Pd nanocubes was one order of magnitude higher than that of Pd octahedra, and comparable to that of the state-of-the-art Pt catalysts.
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TL;DR: This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core-shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts and metal-free catalysts.
Abstract: The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core–shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided.
2,964 citations
TL;DR: The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes, and the design and optimization of air-electrode structure are outlined.
Abstract: Because of the remarkably high theoretical energy output, metal–air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal–air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal–air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic–organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal–air batteries (219 references).
2,211 citations
TL;DR: The most recent advances in the development of Pt-based and Pt-free materials in the field of fuel cell ORR catalysis are reviewed to provide insights into the remaining challenges and directions for future perspectives and research.
Abstract: Developing highly efficient catalysts for the oxygen reduction reaction (ORR) is key to the fabrication of commercially viable fuel cell devices and metal–air batteries for future energy applications. Herein, we review the most recent advances in the development of Pt-based and Pt-free materials in the field of fuel cell ORR catalysis. This review covers catalyst material selection, design, synthesis, and characterization, as well as the theoretical understanding of the catalysis process and mechanisms. The integration of these catalysts into fuel cell operations and the resulting performance/durability are also discussed. Finally, we provide insights into the remaining challenges and directions for future perspectives and research.
1,752 citations
TL;DR: This review focuses on the major obstacle of sluggish kinetics of the cathode in both batteries, and summary the fundamentals and recent advances related to the oxygen catalyst materials, and several future research directions are proposed based on the results achieved.
Abstract: With the development of renewable energy and electrified transportation, electrochemical energy storage will be more important in the future than it has ever been in the past. Although lithium-ion batteries (LIBs) are traditionally considered to be the most likeliest candidate thanks to their relatively long cycle life and high energy efficiency, their limited energy density as well as cost are still causing a bottleneck for their long-term application. Alternatively, metal–air batteries have been proposed as a very promising large-scale electricity storage technology with the replacement of the intercalation reaction mechanism by the catalytic redox reaction of a light weight metal–oxygen couple. Generally, based on the electrolyte, these metal–air batteries can be divided into aqueous and nonaqueous systems, corresponding to two typical batteries of Zn–air and Li–air, respectively. The prominent feature of both batteries are their extremely high theoretical energy density, especially for nonaqueous Li–air batteries, which far exceeds the best that can be achieved with LIBs. In this review, we focus on the major obstacle of sluggish kinetics of the cathode in both batteries, and summarize the fundamentals and recent advances related to the oxygen catalyst materials. According to the electrolyte, the aqueous and nonaqueous electrocatalytic mechanisms of the oxygen reduction and evolution reactions are discussed. Subsequently, seven groups of oxygen catalysts, which have played catalytic roles in both systems, are selectively reviewed, including transition metal oxides (single-metal oxides and mixed-metal oxides), functional carbon materials (nanostructured carbons and doped carbons), metal oxide–nanocarbon hybrid materials, metal–nitrogen complexes (non-pyrolyzed and pyrolyzed), transition metal nitrides, conductive polymers, and precious metals (alloys). Nonaqueous systems have the advantages of energy density and rechargeability over aqueous systems and have gradually become the research focus of metal–air batteries. However, there are considerable challenges beyond catalysts from aqueous to nonaqueous electrolytes, which are also discussed in this review. Finally, several future research directions are proposed based on the results achieved in this field, with emphasis on nonaqueous Li–air batteries.
1,186 citations
TL;DR: This Perspective provides a contemporary understanding of the shape evolution of colloidal metal nanocrystals under thermodynamically and kinetically controlled conditions and extends the mechanistic insights learnt to account for the products of conventional one-pot syntheses that involve self-nucleation only.
Abstract: This Perspective provides a contemporary understanding of the shape evolution of colloidal metal nanocrystals under thermodynamically and kinetically controlled conditions. It has been extremely challenging to investigate this subject in the setting of one-pot synthesis because both the type and number of seeds involved would be changed whenever the experimental conditions are altered, making it essentially impossible to draw conclusions when comparing the outcomes of two syntheses conducted under different conditions. Because of the uncertainty about seeds, most of the mechanistic insights reported in literature for one-pot syntheses of metal nanocrystals with different shapes are either incomplete or ambiguous, and some of them might be misleading or even wrong. Recently, with the use of well-defined seeds for such syntheses, it became possible to separate growth from nucleation and therefore investigate the explicit role(s) played by a specific thermodynamic or kinetic parameter in directing the evolution of colloidal metal nanocrystals into a specific shape. Starting from single-crystal seeds enclosed by a mix of {100}, {111}, and {110} facets, for example, one can obtain colloidal nanocrystals with diversified shapes by adjusting various thermodynamic or kinetic parameters. The mechanistic insights learnt from these studies can also be extended to account for the products of conventional one-pot syntheses that involve self-nucleation only. The knowledge can be further applied to many other types of seeds with twin defects or stacking faults, making it an exciting time to design and synthesize colloidal metal nanocrystals with the shapes sought for a variety of fundamental studies and technologically important applications.
707 citations
References
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TL;DR: In this paper, the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations was analyzed and a detailed description of the free energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias was presented.
Abstract: We present a method for calculating the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations. We used that method in combination with detailed density functional calculations to develop a detailed description of the free-energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias. This allowed us to identify the origin of the overpotential found for this reaction. Adsorbed oxygen and hydroxyl are found to be very stable intermediates at potentials close to equilibrium, and the calculated rate constant for the activated proton/electron transfer to adsorbed oxygen or hydroxyl can account quantitatively for the observed kinetics. On the basis of a database of calculated oxygen and hydroxyl adsorption energies, the trends in the oxygen reduction rate for a large number of different transition and noble metals can be accounted for. Alternative reaction mechanisms involving proton/electron transfer to ...
7,711 citations
TL;DR: In this article, the authors quantified the activities and voltage loss modes for state-of-the-art MEAs (membrane electrode assemblies), specifies performance goals needed for automotive application, and provides benchmark oxygen reduction activities for state of the art platinum electrocatalysts.
Abstract: The mass production of proton exchange membrane (PEM) fuel-cell-powered light-duty vehicles requires a reduction in the amount of Pt presently used in fuel cells. This paper quantifies the activities and voltage loss modes for state-of-the-art MEAs (membrane electrode assemblies), specifies performance goals needed for automotive application, and provides benchmark oxygen reduction activities for state-of-the-art platinum electrocatalysts using two different testing procedures to clearly establish the relative merit of candidate catalysts. A pathway to meet the automotive goals is charted, involving the further development of durable, high-activity Pt-alloy catalysts. The history, status in recent experiments, and prospects for Pt-alloy cathode catalysts are reviewed. The performance that would be needed for a cost-free non-Pt catalyst is defined quantitatively, and the behaviors of several published non-Pt catalyst systems (and logical extensions thereof), are compared to these requirements. Critical research topics are listed for the Pt-alloy catalysts, which appear to represent the most likely route to automotive fuel cells.
4,298 citations
TL;DR: It is demonstrated that the Pt3Ni( 111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-foldMore active than the current state-of-the-art Pt/C catalysts for PEMFC.
Abstract: The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption.
3,804 citations
Book•
01 Mar 2003
TL;DR: In this article, the authors present a survey of fuel cell technologies and applications, focusing on hydrogen storage, hydrogen generation, and other energy conversion related topics, as well as their applications.
Abstract: VOLUME 1: FUNDAMENTALS AND SURVEY OF SYSTEMS. Contributors to Volume 1. Foreword. Preface. Abbreviations and Acronyms. Part 1: Thermodynamics and kinetics of fuel cell reactions. Part 2: Mass transfer in fuel cells. Part 3: Heat transfer in fuel cells. Part 4: Fuel cell principles, systems and applications. Contents for Volumes 2, 3 and 4. Subject Index. VOLUME 2: ELECTROCATALYSIS. Contributors to Volume 2. Foreword. Preface. Abbreviations and Acronyms. Part 1: Introduction. Part 2: Theory of electrocatalysis. Part 3: Methods in electrocatalysis. Part 4: The hydrogen oxidation/evolution reaction. Part 5: The oxygen reduction/evolution reaction. Part 6: Oxidation of small organic molecules. Part 7: Other energy conversion related topics. Contents for Volumes 1, 3 and 4. Subject Index. VOLUME 3: FUEL CELL TECHNOLOGY AND APPLICATIONS: PART 1. Contributors to Volumes 3 and 4. Foreword. Preface. Abbreviations and Acronyms. Part 1: Sustainable energy supply. Part 2: Hydrogen storage and hydrogen generation. Development prospects for hydrogen storage. Chemical hydrogen storage devices. Reforming of methanol and fuel processor development. Fuel processing from hydrocarbons to hydrogen. Well-to-wheel efficiencies. Hydrogen safety, codes and standards. Part 3: Polymer electrolyte membrane fuel cell systems (PEMFC). Bipolar plate materials and flow field design. Membrane materials. Electro-catalysts. Membrane-electrode-assembly (MEA). State-of-the-art performance and durability. VOLUME 4: FUEL CELL TECHNOLOGY AND APPLICATIONS, PART 2. Contributors to Volume 3 and 4. Foreword. Preface. Abbreviations and Acronyms. Part 3: Polymer electrolyte membrane fuel cells and systems (PEMFC) (Continued from previous volume). System design and system-specific aspects. Air-supply components. Applications based on PEM-technology. Part 4: Alkaline fuel cells and systems (AFC). Part 5: Phosphoric acid fuel cells and systems (PAFC). Part 6: Direct methanol fuel cells and systems (DMFC). Part 7: Molten carbonate fuel cells and systems (MCFC). Part 8: Solid oxide fuel cells and systems (SOFC). Materials. Stack and system design. New concepts. Part 9: Primary and secondary metal/air cells. Part 10: Portable fuel cell systems. Part 11: Current fuel cell propulsion systems. PEM fuel cell systems for cars/buses. PEM fuel cell systems for submarines. AFC fuel cell systems. Part 12: Electric utility fuel cell systems. Part 13: Future prospects of fuel cell systems. Contents for Volumes 1 and 2. Subject Index.
2,917 citations
TL;DR: In this article, a review of recent progress in the development of the oxygen reduction reaction (ORR) catalysis on well-defined surfaces is presented, focusing on two type of metallic surfaces: platinum single crystals and bimetallic surfaces based on platinum.
Abstract: In this review we selectively summarize recent progress, primarily from our laboratory, in the development of the oxygen reduction reaction (ORR) catalysis on well-defined surfaces. The focus is on two type of metallic surfaces: platinum single crystals and bimetallic surfaces based on platinum. The single crystal results provide insight into the effects of the platinum structure on the kinetics of the ORR, and create a fundamental link between the specific activity of Pt (rate per unit area) and particle size (for various particle shapes). The results show that the structure sensitive kinetics of the ORR arise primarily due to structure sensitive adsorption of anions. In the absence of specific adsorption, such as in Nafion polymer electrolyte, no particle size effect is expected. The knowledge of the electrocatalysis of the ORR on model bimetallic surfaces on Pt-Ni and Pt-Co bulk alloys was used to resolve the enhanced ORR kinetics on supported Pt-Ni and Pt-Co catalysts. Finally, we show that the ORR on platinum modified with pseudomorphic Pd metal film in alkaline solution is the best catalysts ever used in O2 reduction. For both bimetallic systems, we demonstrated that the ability to make a controlled and well characterized arrangement of two elements in the electrode surface region presage a new era of advances in the ORR electrocatalysis.
991 citations