Ir-Catalysed Nitrous Oxide (N2O) Decomposition:Effect of Ir Particle Size and Metal–Support Interactions

The effect of the morphology of Ir particles supported on γ-Al2O3, 8 mol%Y2O3-stabilized ZrO2 (YSZ), 10 mol%Gd2O3-doped CeO2 (GDC) and 80 wt%Al2O3–10 wt%CeO2–10 wt%ZrO2 (ACZ) on their stability on oxidative conditions, the associated metal–support interactions and activity for catalytic decomposition of N2O has been studied. Supports with intermediate or high oxygen ion lability (GDC and ACZ) effectively stabilized Ir nanoparticles against sintering, in striking contrast to supports offering negligible or low oxygen ion lability (γ-Al2O3 and YSZ). Turnover frequency studies using size-controlled Ir particles showed strong structure sensitivity, de-N2O catalysis being favoured on large catalyst particles. Although metallic Ir showed some de-N2O activity, IrO2 was more active, possibly present as a superficial overlayer on the iridium particles under reaction conditions. Support-induced turnover rate modifications, resulted from an effective double layer [Oδ−–δ+](Ir) on the surface of iridium nanoparticles, via O2− backspillover from the support, were significant in the case of GDC and ACZ

Bio-inspired nanocatalysts for the oxygen reduction reaction

Electrochemical conversions at fuel cell electrodes are complex processes. In particular, the oxygen reduction reaction has substantial overpotential limiting the electrical power output efficiency. Effective and inexpensive catalytic interfaces are therefore essential for increased performance. Taking inspiration from enzymes, earth-abundant metal centres embedded in organic environments present remarkable catalytic active sites. Here we show that these enzyme-inspired centres can be effectively mimicked in two-dimensional metal-organic coordination networks self-assembled on electrode surfaces. Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine coordinating to single iron and manganese atoms on Au(111) effectively catalyse the reduction and reveal distinctive catalytic activity in alkaline media. These results demonstrate the potential of surface-engineered metal-organic networks for electrocatalytic conversions. Specifically designed coordination complexes at surfaces inspired by enzyme cofactors represent a new class of nanocatalysts with promising applications in electrocatalysis.Fil: Grumelli, Doris Elda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Max Planck Institute for Solid State Research; AlemaniaFil: Wurtser, Benjamin. Max Planck Institute for Solid State Research; AlemaniaFil: Stepanow, Sabastian. Max Planck Institute for Solid State Research; AlemaniaFil: Kern, Klaus. Max Planck Institute for Solid State Research; Alemania. Ecole Polytechnique Federale de Lausanne; Suiz

General Minimal Flavor Violation

A model independent study of the minimal flavor violation (MFV) framework is presented, where the only sources of flavor breaking at low energy are the up and down Yukawa matrices. Two limits are identified for the Yukawa coupling expansion: linear MFV, where it is truncated at the leading terms, and nonlinear MFV, where such a truncation is not possible due to large third generation Yukawa couplings. These are then resummed to all orders using non-linear sigma-model techniques familiar from models of collective breaking. Generically, flavor diagonal CP violating (CPV) sources in the UV can induce O(1) CPV in processes involving third generation quarks. Due to a residual U(2) symmetry, the extra CPV in B_d-\bar B_d mixing is bounded by CPV in B_s-\bar B_s mixing. If operators with right-handed light quarks are subdominant, the extra CPV is equal in the two systems, and is negligible in processes involving only the first two generations. We find large enhancements in the up type sector, both in CPV in D-\bar D mixing and in top flavor violation.Comment: 5 pages and no figure

Representing 3D Space in Working Memory: Spatial Images from Vision, Hearing, Touch, and Language

The chapter deals with a form of transient spatial representation referred to as a spatial image. Like a percept, it is externalized, scaled to the environment, and can appear in any direction about the observer. It transcends the concept of modality, as it can be based on inputs from the three spatial senses, from language, and from long-term memory. Evidence is presented that supports each of the claimed properties of the spatial image, showing that it is quite different from a visual image. Much of the evidence presented is based on spatial updating. A major concern is whether spatial images from different input modalities are functionally equivalent— that once instantiated in working memory, the spatial images from different modalities have the same functional characteristics with respect to subsequent processing, such as that involved in spatial updating. Going further, the research provides some evidence that spatial images are amodal (i.e., do not retain modality-specific features)