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 ...

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Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode

BACKGROUND With a rising global population, increasing energy demands, and impending climate change, major concerns have been raised over the security of our energy future. Developing sustainable, fossil-free pathways to produce fuels and chemicals of global importance could play a major role in reducing carbon dioxide emissions while providing the feedstocks needed to make the products we use on a daily basis. One prospective goal is to develop electrochemical conversion processes that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable energy. Electrocatalysts play a key role in these energy conversion technologies because they increase the rate, efficiency, and selectivity of the chemical transformations involved. Today’s electrocatalysts, however, are inadequate. The grand challenge is to develop advanced electrocatalysts with the enhanced performance needed to enable widespread penetration of clean energy technologies. ADVANCES Over the past decade, substantial progress has been made in understanding several key electrochemical transformations, particularly those that involve water, hydrogen, and oxygen. The combination of theoretical and experimental studies working in concert has proven to be a successful strategy in this respect, yielding a framework to understand catalytic trends that can ultimately provide rational guidance toward the development of improved catalysts. Catalyst design strategies that aim to increase the number of active sites and/or increase the intrinsic activity of each active site have been successfully developed. The field of hydrogen evolution, for example, has seen important breakthroughs over the years in the development of highly active non–precious metal catalysts in acid. Notable advancements have also been made in the design of oxygen reduction and evolution catalysts, although there remains substantial room for improvement. The combination of theory and experiment elucidates the remaining challenges in developing further improved catalysts, often involving scaling relations among reactive intermediates. This understanding serves as an initial platform to design strategies to circumvent technical obstacles, opening up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions. OUTLOOK A systematic framework of combining theory and experiment in electrocatalysis helps to uncover broader governing principles that can be used to understand a wide variety of electrochemical transformations. These principles can be applied to other emerging and promising clean energy reactions, including hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, among others. Although current paradigms for catalyst development have been helpful to date, a number of challenges need to be successfully addressed in order to achieve major breakthroughs. One important frontier, for example, is the development of both experimental and computational methods that can rapidly elucidate reaction mechanisms on broad classes of materials and in a wide range of operating conditions (e.g., pH, solvent, electrolyte). Such efforts would build on current frameworks for understanding catalysis to provide the deeper insights needed to fine-tune catalyst properties in an optimal manner. The long-term goal is to continue improving the activity and selectivity of these catalysts in order to realize the prospects of using renewable energy to provide the fuels and chemicals that we need for a sustainable energy future.

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Combining theory and experiment in electrocatalysis: Insights into materials design

The shapes of noble metal nanocrystals (NCs) are usually defined by polyhedra that are enclosed by {111} and {100} facets, such as cubes, tetrahedra, and octahedra. Platinum NCs of unusual tetrahexahedral (THH) shape were prepared at high yield by an electrochemical treatment of Pt nanospheres supported on glassy carbon by a square-wave potential. The single-crystal THH NC is enclosed by 24 high-index facets such as {730}, {210}, and/or {520} surfaces that have a large density of atomic steps and dangling bonds. These high-energy surfaces are stable thermally (to 800°C) and chemically and exhibit much enhanced (up to 400%) catalytic activity for equivalent Pt surface areas for electro-oxidation of small organic fuels such as formic acid and ethanol.

Synthesis of Tetrahexahedral Platinum Nanocrystals with High-Index Facets and High Electro-Oxidation Activity

Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K2PtCl4 with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

http://www.ifc.dicp.ac.cn/library/cailiao/pdf1/19.pdf

Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

Liming Dai,*,†,‡ Yuhua Xue,†,‡ Liangti Qu,* Hyun-Jung Choi, and Jong-Beom Baek* †Center of Advanced Science and Engineering for Carbon (Case4Carbon), Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106, United States Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Department of Chemistry, School of Science, Beijing Institute of Technology, Beijing 100081, People’s Republic of China School of Energy and Chemical Engineering/Center for Dimension-Controllable Covalent Organic Frameworks, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon, Ulsan, 689-798, South Korea

Metal-free catalysts for oxygen reduction reaction.

Structural effects in electrocatalysis: oxygen reduction on platinum low index single-crystal surfaces in perchloric acid solutions

Determination of the kinetic parameters of the oxygen reduction reaction using the rotating ring-disk electrode: Part II. Applications☆

Studies of chemical reactions on well-defined surfaces provide fundamental data on surface reactivity and guidelines for the understanding and design of catalytic materials but few such studies have been done in electrocatalysis. We report here a study of the oxidation kinetics of HCOOH, CH3OH and CH2O on single crystal platinum electrodes with (100), (110) and (111) orientations. Pronounced dependence of the kinetics of these reactions on the crystallographic orientation of the surface has been found. The potential regions where reactions take place, the peaks of voltammetry curves, and the magnitude of currents at the peaks are different for each plane. These differences are explained on the basis of adsorption of a strongly bound intermediate, which shows a pronounced dependence on the symmetry of the single crystal planes. This intermediate completely blocks the Pt (100) surface; the smallest adsorption is at the (111) plane. On activation, the (100) surface shows the highest activity. These results suggest that electrocatalytic reactions exhibit structural sensitivity. They also provide guidelines for designing catalysts for the oxidation of small organic molecules to be used in electrochemical energy conversion.

R.R. Adžić

Papers

Structural effects in electrocatalysis: oxygen reduction on platinum low index single-crystal surfaces in perchloric acid solutions

Determination of the kinetic parameters of the oxygen reduction reaction using the rotating ring-disk electrode: Part II. Applications☆

Structural effects in electrocatalysis

Electrosorption of hydrogen and sulphuric acid anions on single-crystal platinum stepped surfaces: Part I. The [110] zone

Electrocatalysis of oxygen on single crystal gold electrodes