Factors controlling the energetics of the oxygen reduction reaction on the Pd-Co electro-catalysts: Insight from first principles

We report here results of our density functional theory based computational studies of the electronic structure of the Pd-Co alloy electrocatalysts and energetics of the oxygen reduction reaction (ORR) on their surfaces. The calculations have been performed for the (111) surfaces of pure Pd, Pd0.75Co0.25 and Pd0.5Co0.5 alloys, as well as of the surface segregated Pd/Pd0.75Co0.25 alloy. We find the hybridization of dPd and dCo electronic states to be the main factor controlling the electrocatalytic properties of Pd/Pd0.75Co0.25. Namely the dPd - dCo hybridization causes low energy shift of the surface Pd d-band with respect to that for Pd(111). This shift weakens chemical bonds between the ORR intermediates and the Pd/Pd0.75Co0.25 surface, which is favorable for the reaction. Non-segregated Pd0.75Co0.25 and Pd0.5Co0.5 surfaces are found to be too reactive for ORR due to bonding of the intermediates to the surface Co atoms. Analysis of the ORR free energy diagrams, built for the Pd and Pd/Pd0.75Co0.25, shows that the co-adsorption of the ORR intermediates and water changes the ORR energetics significantly and makes ORR more favorable. We find the onset ORR potential estimated for the configurations with the O - OH and OH - OH co-adsorption to be in very good agreement with experiment. The relevance of this finding to the real reaction environment is discussed

Single Platinum Atoms Electrocatalysts: Oxygen Reduction and Hydrogen Oxidation Reactions

Atomically dispersed catalyst consisting of Pt atoms arranged in a c(2 × 2) array on RuO2(110) substrate was prepared. A large interatomic distance of Pt atoms in a c(2 × 2) phase precludes the reactants to interact with more than one Pt atoms. A strong bond of Pt atoms with RuO2 prevents agglomeration of Pt atoms to form 2D-islands or 3D-clusters. Activities of single Pt atom catalyst for the oxygen reduction and hydrogen oxidation reactions were determined and compared with those of bulk Pt. It has lower catalytic activity for the oxygen reduction reaction and similar activity for hydrogen oxidation reaction compared to Pt(111). This was explained by a large calculated up-shift of the d-band center of Pt atoms and larger Pt-Pt interatomic distance than that of Pt(111). This information is of considerable interest for further development of electrocatalysis. This work is licensed under a Creative Commons Attribution 4.0 International License

High CO tolerance of Pt/Ru nano-catalyst: insight from first principles calculation

Density functional theory based calculations of the energetics of adsorption and diffusion of CO on Pt islets and on the Ru(0001) substrate show that CO has the lowest adsorption energy at the center of the islet, and its bonding increases as it moves to the edge of the island and further onto the substrate. Activation energy barriers for CO diffusion from the islet to the Ru surface are found to be lower than 0.3 eV making the process feasible and leading to the conclusion that this hydrogen oxidation catalyst is CO tolerant because of the spillover of CO from active Pt sites to the Ru substrate. We present the rationale for this effect using insights from detailed electronic structure calculations.Comment: 6 pages, 5 figure

Recent Advances in Developing Platinum Monolayer Electrocatalysts for the O2 Reduction Reaction

For Pt, the best single-element catalyst for many reactions, the question of content and loading is exceedingly important because of its price and availability. Using platinum as a fuel-cell catalyst in automotive applications will cause an unquantifiable increase in the demand for this metal. This big obstacle for using fuel cells in electric cars must be solved by decreasing the content of Pt, which is a great challenge of electrocatalysis Over the last several years we inaugurated a new class of electrocatalysts for the oxygen reduction reaction (ORR) based on a monolayer of Pt deposited on metal or alloy carbon-supported nanoparticles. The possibility of decreasing the Pt content in the ORR catalysts down to a monolayer level has a considerable importance because this reaction requires high loadings due to its slow kinetics. The Pt-monolayer approach has several unique features and some of them are: high Pt utilization, enhanced (or decreased) activity, enhanced stability, and direct activity correlations. The synthesis of Pt monolayer (ML) electrocatalysts was facilitated by our new synthesis method which allowed us to deposit a monolayer of Pt on various metals, or alloy nanoparticles [1, 2] for the cathode electrocatalyst. In this synthesis approach Pt is laid down by the galvanically displacing a Cu monolayer, which was deposited at underpotentials in a monolayer-limited reaction on appropriate metal substrate, with Pt after immersing the electrode in a K{sub 2}PtCl{sub 4} solution

Implementation and performance of the Detector Control System for the electromagnetic calorimeter of the CMS experiment

In this presentation we describe the main design objectives, the detailed specifications and the final layout of the Detector Control System (DCS) for the electromagnetic calorimeter (ECAL) of the CMS experiment. Emphasis is put on the system implementation and specific hardware and software solutions in each of its sub-systems. The latest results from the tests of final prototypes of these subsystems during the 2006 ECAL test-beam programme, as well as the installation and commissioning of the whole DCS at the CMS experimental construction site are discussed

Reaction Kinetics and X-Ray Absorption Spectroscopy Studies of Yttrium Containing Metal Hydride Electrodes

This was a study of electrode degradation mechanisms and the reaction kinetics of LaNi{sub 4.7}Sn{sub 0.3}, La{sub (1{minus}x)} Y{sub x}Ni{sub 4.7}Sn{sub 0.3} (x = 0.1, 0.2, and 0.3) and La{sub 0.7}Y{sub 0.3}Ni{sub 4.6}Sn{sub 0.3}Co{sub 0.1} metal hydride electrodes. Alloy characterization included x-ray diffraction (XRD), x-ray absorption (XAS), hydrogen absorption in a Sieverts apparatus, and electrochemical cycling of alloy electrodes. The atomic volume of H was determined for two of the alloys. Electrochemical kinetic measurements were made using steady state galvanostatic measurements, galvanodynamic sweep, and electrochemical impedance techniques. XAS was used to examine the degree of corrosion of the alloys with cycling. Alloying with Y decreased the corrosion rate. The results are consistent with corrosion inhibition by a Y containing passive film. The increase in the kinetics of the hydrogen oxidation reaction (HOR) with increasing depth of discharge was much greater on the Y containing alloys. This may be due to the dehydriding of the catalytic species on the surface of the metal hydride particles

A Large Hadron Electron Collider at CERN

This document provides a brief overview of the recently published report on the design of the Large Hadron Electron Collider (LHeC), which comprises its physics programme, accelerator physics, technology and main detector concepts. The LHeC exploits and develops challenging, though principally existing, accelerator and detector technologies. This summary is complemented by brief illustrations of some of the highlights of the physics programme, which relies on a vastly extended kinematic range, luminosity and unprecedented precision in deep inelastic scattering. Illustrations are provided regarding high precision QCD, new physics (Higgs, SUSY) and electron-ion physics. The LHeC is designed to run synchronously with the LHC in the twenties and to achieve an integrated luminosity of O(100) fb$^{-1}$. It will become the cleanest high resolution microscope of mankind and will substantially extend as well as complement the investigation of the physics of the TeV energy scale, which has been enabled by the LHC

Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9a�...V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity.open251

Radiation hardness qualification of PbWO4 scintillation crystals for the CMS Electromagnetic Calorimeter

This is the Pre-print version of the Article. The official published version can be accessed from the link below - Copyright @ 2010 IOPEnsuring the radiation hardness of PbWO4 crystals was one of the main priorities during the construction of the electromagnetic calorimeter of the CMS experiment at CERN. The production on an industrial scale of radiation hard crystals and their certification over a period of several years represented a difficult challenge both for CMS and for the crystal suppliers. The present article reviews the related scientific and technological problems encountered