The development of hydrogen-based energy sources as viable alternatives to fossil-fuel technologies has revolutionized clean energy production using fuel cells. However, to date, the slow rate of the hydrogen oxidation reaction (HOR) in alkaline environments has hindered advances in alkaline fuel cell systems. Here, we address this by studying the trends in the activity of the HOR in alkaline environments. We demonstrate that it can be enhanced more than fivefold compared to state-of-the-art platinum catalysts. The maximum activity is found for materials (Ir and Pt₀.₁Ru₀.₉) with an optimal balance between the active sites that are required for the adsorption/dissociation of H₂ and for the adsorption of hydroxyl species (OHad). We propose that the more oxophilic sites on Ir (defects) and PtRu material (Ru atoms) electrodes facilitate the adsorption of OHad species. Those then react with the hydrogen intermediates (Had) that are adsorbed on more noble surface sites.

Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

We report the design and synthesis of multimetallic Au/Pt-bimetallic nanoparticles as a highly durable electrocatalyst for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. This system was first studied on well-defined Pt and FePt thin films deposited on a Au(111) surface, which has guided the development of novel synthetic routes toward shape-controlled Au nanoparticles coated with a Pt-bimetallic alloy. It has been demonstrated that these multimetallic Au/FePt(3) nanoparticles possess both the high catalytic activity of Pt-bimetallic alloys and the superior durability of the tailored morphology and composition profile, with mass-activity enhancement of more than 1 order of magnitude over Pt catalysts. The reported synergy between well-defined surfaces and nanoparticle synthesis offers a persuasive approach toward advanced functional nanomaterials.

Monodisperse and homogeneous PtxNi1‐x alloy nanoparticles of various compositions are synthesized via an organic solution approach in order to reveal the correlation between surface chemistry and their electrocatalytic properties. Atomic‐level microscopic analysis of the compositional profile and modeling of nanoparticle structure are combined to follow the dependence of Ni dissolution on the initial alloy composition and formation of the Pt‐skeleton nanostructures. The developed approach and acquired knowledge about surface structure‐property correlation can be further generalized and applied towards the design of advanced functional nanomaterials.

Monodisperse Pt3Co nanoparticles with size controlled from 3 to 9 nm have been synthesized through an organic solvothermal approach and applied as electrocatalysts for the oxygen reduction reaction. Electrochemical study shows that the Pt3Co nanoparticles are highly active for the oxygen reduction reaction and the activity is size-dependent. The optimal size for maximal mass activity was established to be around 4.5 nm by balancing the electrochemically active surface area and specific activity.

Design of active and stable Pt-based nanoscale electrocatalysts for the oxygen reduction reaction (ORR) will be the key to improving the efficiency of fuel cells that are needed to deliver reliable, affordable and environmentally friendly energy. Here, by exploring the ORR on Pt single crystals, cubo-octahedral (polyhedral) Pt NPs with different sizes (ranging from 2 to 7 nm), and 7-8 nm Pt NPs with different shapes (cubo-octahedral vs. cube vs. octahedral), we presented surface science approach capable of rationalizing, and ultimately understanding, fundamental relationships between stability of Pt NPs and activity of the ORR in acidic media. By exploring the potential induced dissolution/re-deposition of Pt between 0.05 and 1.3 V, we found that concomitant variations in morphology of Pt(111) and Pt(100) lead to narrowing differences in activity between Pt single crystal surfaces. We also found that regardless of an initial size or shape, NPs are metastable and easily evolve to thermodynamically equilibrated shape and size with very similar activity for the ORR. We concluded that while initially clearly observed, the particle size and shape effects diminish as the particles age to the point that it may appear that the ORR depends neither on the particle size nor particle shape. IntroductionThe last two decades have witnessed remarkable progress in our ability to chemically synthesize metal nanoparticles (NPs) ranging in size from 1 to 10 nm with unique electrocatalytic properties. 1-4 Because the electronic properties of metal NPs in this size range are not unique, 5 (electro)catalyst research with such materials has focused on the variations in the reaction rate or selectivity with characteristic dimensions of metallic catalysts. While Boronin and co-workers 6 pioneered this approach to understand the "crystalline size effect" in heterogeneous catalysis, Kinoshita 7 and others 8,9 used this tactic to understand the "particle size effect" in electrocatalysis. There is no simple ideal structure that will model all the aspects of NP catalysts, particularly in the configuration that are used in electrolytic cells. However, if one considers the equilibrium shape of a face-centered cubic (fcc) metal NP such as a cubooctahedron, consisting of (111) and (100) facets bounded by edge atom rows that are like the topmost rows in the (110) surface, single-crystal surfaces may serve as a reasonable model for

The development of electrocatalytic materials of enhanced activity and efficiency through careful manipulation, at the atomic scale, of the catalyst surface structure has long been a goal of electrochemists. To accomplish this ambitious objective, it would be necessary both to obtain a thorough understanding of the relationship between the atomic-level surface structure and the catalytic properties and to develop techniques to synthesize and stabilize desired active sites. In this contribution, we present a combined experimental and theoretical study in which we demonstrate how this approach can be used to develop novel, platinum-based electrocatalysts for the CO electrooxidation reaction in CO(g)-saturated solution; the catalysts show activities superior to any pure-metal catalysts previously known. We use a broad spectrum of electrochemical surface science techniques to synthesize and rigorously characterize the catalysts, which are composed of adisland-covered platinum surfaces, and we show that highly undercoordinated atoms on the adislands themselves are responsible for the remarkable activity of these materials.

Improving the efficiency of electrocatalytic reduction of oxygen represents one of the main challenges for the development of renewable energy technologies. Here, we report the systematic evaluation of Pt-ternary alloys (Pt3(MN)1 with M, N = Fe, Co, or Ni) as electrocatalysts for the oxygen reduction reaction (ORR). We first studied the ternary systems on extended surfaces of polycrystalline thin films to establish the trend of electrocatalytic activities and then applied this knowledge to synthesize ternary alloy nanocatalysts by a solvothermal approach. This study demonstrates that the ternary alloy catalysts can be compelling systems for further advancement of ORR electrocatalysis, reaching higher catalytic activities than bimetallic Pt alloys and improvement factors of up to 4 versus monometallic Pt.