Size and Site Dependence of the Catalytic Activity of Iridium Clusters towards Ethane Dehydrogenation

This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Irn (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Irn + C2H6 → H−Irn−C2H5 → (H)2−Irn−C2H4, the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir8 is the least reactive towards H-elimination in ethane: Ir8 + C2H6 → H−Ir8−C2H5 has a large (65 kJ/mol) energy barrier, whereas Ir12 (3×2×2 cuboid) and Ir18 (3×3×2 cuboid) lower this energy barrier to 22 kJ/mol and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir18 + C2H6 → H−Ir18−C2H5 reaction is 3 kJ/mol, 48 kJ/mol, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C–H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Irn + C2H6 + ½ O2 → Irn + C2H4 + H2O. These results will be useful towards reducing the energy cost of ethane dehydrogenation in industry

Atmospheric effects of the emerging mainland Chinese transportation system at and beyond the regional scale

Local surface travel needs in the People's Republic of China (mainland China) have traditionally been met largely by nonpolluting bicycles. A major automobile manufacturing/importing effort has begun in the country over the last decade, and planning documents indicate that the Chinese may strive to acquire more than 100 million vehicles early in the next century. By analogy with large automotive fleets already existing in the western world, both regional and global scale pollution effects are to be expected from the increase. The present work adopts the latest projections of Chinese automobile manufacture and performs some quantitative assessments of the extent of pollution generation. Focus for the investigation is placed upon the oxidant ozone. Emissions of the precursor species nitrogen oxides and volatile organics are constructed based on data for the current automotive sector in the eastern portion of the United States. Ozone production is first estimated from measured values for continental/oceanic scale yields relative to precursor oxidation. The estimates are then corroborated through idealized two dimensional modeling of the photochemistry taking place in springtime air flow off the Asian land mass and toward the Pacific Ocean. The projected fleet sizes could increase coastal and remote oceanic ozone concentrations by tens of parts per billion (ppb) in the lower troposphere. Influences on the tropospheric aerosol system and on the major greenhouse gas carbon dioxide are treated peripherally. Nitrogen oxides created during the vehicular internal combustion process will contribute to nitrate pollution levels measured in the open Pacific. The potential for soot and fugitive dust increases should be considered as the automotive infrastructure develops. Since the emerging Chinese automotive transportation system will represent a substantial addition to the global fleet and all the carbon in gasoline is eventually oxidized completely, a significant rise in global carbon dioxide inputs will ensue as well. Some policy issues are treated preliminary. The assumption is made that alterations to regional oxidant/aerosol systems and to terrestrial climate are conceivable. The likelihood that the Chinese can achieve the latest vehicle fleet goals is discussed, from the points of view of new production, positive pollution feedbacks from a growing automobile industry, and known petroleum reserves. Vehicular fuel and maintenance options lying before the Chinese are outlines and compared. To provide some perspective on the magnitude of the environmental changes associated with an Asian automotive buildup, recent estimates of the effects of future air traffic over the Pacific Rim are described

Towards an Ontological Modelling of Preference Relations

Preference relations are intensively studied in Economics, but they are also approached in AI, Knowledge Representation, and Conceptual Modelling, as they provide a key concept in a variety of domains of application. In this paper, we propose an ontological foundation of preference relations to formalise their essential aspects across domains. Firstly, we shall discuss what is the ontological status of the relata of a preference relation. Secondly, we investigate the place of preference relations within a rich taxonomy of relations (e.g. we ask whether they are internal or external, essential or contingent, descriptive or nondescriptive relations). Finally, we provide an ontological modelling of preference relation as a module of a foundational (or upper) ontology (viz. OntoUML). The aim of this paper is to provide a sharable foundational theory of preference relation that foster interoperability across the heterogeneous domains of application of preference relations

Could Public Restrooms Be an Environment for Bacterial Resistomes?

PMCID: PMC3547874This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited

Ecological implications of fine-scale fire patchiness and severity in tropical savannas of northern Australia

Research ArticleUnderstanding fine-scale fire patchiness has significant implications for ecological processes and biodiversity conservation. It can affect local extinction of and recolonisation by relatively immobile fauna and poorly seed-dispersed flora in fire-affected areas. This study assesses fine-scale fire patchiness and severity, and associated implications for biodiversity, in north Australian tropical savanna systems. We used line transects to sample burning patterns of ground layer vegetation in different seasons and vegetation structure types, within the perimeter of 35 fires that occurred between 2009 and 2011. We evaluated two main fire characteristics: patchiness (patch density and mean patch length) and severity (inferred from char and scorch heights, and char and ash proportions). The mean burned area of ground vegetation was 83 % in the early dry season (EDS: May to July) and 93 % in the late dry season (LDS: August to November). LDS fires were less patchy (smaller and fewer unburned patches), and had higher fire severity (higher mean char and scorch heights, and twice the proportion of ash) than EDS fires. Fire patchiness varied among vegetation types, declining under more open canopy structure. The relationship between burned area and fire severity depended on season, being strongly correlated in the EDS and uncorrelated in the LDS. Simulations performed to understand the implications of patchiness on the population dynamics of fire-interval sensitive plant species showed that small amounts of patchiness substantially enhance survival. Our results indicate that the ecological impacts of high frequency fires on firesensitive regional biodiversity elements are likely to be lower than has been predicted from remotely sensed studies that are based on assumptions of homogeneous burninginfo:eu-repo/semantics/publishedVersio

A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting

One of the key-principles of the iron-sulphur world theory is to bring organic molecules close enough to interact with each other, using the surface of pyrite as a substrate in a hydrothermal setting. The present paper explores the relationship of pyrite and organic matter in a hydrothermal setting from the geological record; in hydrothermal calcite veins from Carboniferous limestones in central Ireland. Here, the organic matter is accumulated as coatings around, and through, pyrite grains. Most of the pyrite grains are euhedral-subhedral crystals, ranging in size from ca 0.1-0.5 mm in diameter, and they are scattered throughout the matrix of the vein calcite. The organic matter was deposited from a hydrothermal fluid at a temperature of at least 200°C, and gives a Raman signature of disordered carbon. This study points to an example from a hydrothermal setting in the geological record, demonstrating that pyrite can have a high potential for the concentration and accumulation of organic materials