Alumina-supported Pd-Ag catalysts for low-temperature CO and methanol oxidation

Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate

The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

We report rate coefficients for the relaxation of OH(v = 1) and OD(v = 1) by H2O and D2O as a function of temperature between 251 and 390 K. All four rate coefficients exhibit a negative dependence on temperature. In Arrhenius form, the rate coefficients for relaxation (in units of 10–12 cm3 molecule–1 s–1) can be expressed as: for OH(v = 1) + H2O between 263 and 390 K: k = (2.4 ± 0.9) exp((460 ± 115)/T); for OH(v = 1) + D2O between 256 and 371 K: k = (0.49 ± 0.16) exp((610 ± 90)/T); for OD(v = 1) + H2O between 251 and 371 K: k = (0.92 ± 0.16) exp((485 ± 48)/T); for OD(v = 1) + D2O between 253 and 366 K: k = (2.57 ± 0.09) exp((342 ± 10)/T). Rate coefficients at (297 ± 1 K) are also reported for the relaxation of OH(v = 2) by D2O and the relaxation of OD(v = 2) by H2O and D2O. The results are discussed in terms of a mechanism involving the formation of hydrogen-bonded complexes in which intramolecular vibrational energy redistribution can occur at rates competitive with re-dissociation to the initial collision partners in their original vibrational states. New ab initio calculations on the H2O–HO system have been performed which, inter alia, yield vibrational frequencies for all four complexes: H2O–HO, D2O–HO, H2O–DO and D2O–DO. These data are then employed, adapting a formalism due to Troe (J. Troe, J. Chem. Phys., 1977, 66, 4758), in order to estimate the rates of intramolecular energy transfer from the OH (OD) vibration to other modes in the complexes in order to explain the measured relaxation rates—assuming that relaxation proceeds via the hydrogen-bonded complexes

The Topology of Branching Universes

The purpose of this paper is to survey the possible topologies of branching space-times, and, in particular, to refute the popular notion in the literature that a branching space-time requires a non-Hausdorff topology

ASSOCIATING SNPS WITH BINARY TRAITS

Association mapping uses statistical analyses to test for relationships between genomic markers called single nucleotide polymorphisms (SNPs) and traits. This research focuses on the use of logistic regression to assess the additive, dominance, and epistatic effects when investigating associations between SNPs and binary traits, such as disease status. A very specific phenomenon that results in infinite maximum likelihood estimates (MLEs) of logistic regression parameters, called quasi-separation of points (QSP), is investigated. We provide a solution that relies on the use of Firth’s MLE to estimate logistic regression parameters. Simulated and real data are utilized to investigate the use of Firth’s MLE in a QSP setting

The effect of alongcoast advection on pacific northwest shelf and slope water properties in relation to upwelling variability

The Northern California Current System experiences highly variable seasonal upwelling in addition to larger basin-scale variability, both of which can significantly affect its water chemistry. Salinity and temperature fields from a 7 year ROMS hindcast model of this region (43°N-50°N), along with extensive particle tracking, were used to study interannual variability in water properties over both the upper slope and the midshelf bottom. Variation in slope water properties was an order of magnitude smaller than on the shelf. Furthermore, the primary relationship between temperature and salinity anomalies in midshelf bottom water consisted of variation in density (cold/salty versus warm/fresh), nearly orthogonal to the anomalies along density levels (cold/fresh versus warm/salty) observed on the upper slope. These midshelf anomalies were well-explained (R2=0.6) by the combination of interannual variability in local and remote alongshore wind stress, and depth of the California Undercurrent (CUC) core. Lagrangian analysis of upper slope and midshelf bottom water shows that both are affected simultaneously by large-scale alongcoast advection of water through the northern and southern boundaries. The amplitude of anomalies in bottom oxygen and dissolved inorganic carbon (DIC) on the shelf associated with upwelling variability are larger than those associated with typical variation in alongcoast advection, and are comparable to observed anomalies in this region. However, a large northern intrusion event in 2004 illustrates that particular, large-scale alongcoast advection anomalies can be just as effective as upwelling variability in changing shelf water properties on the interannual scale

The future of Earth observation in hydrology

In just the past 5 years, the field of Earth observation has progressed beyond the offerings of conventional space-agency-based platforms to include a plethora of sensing opportunities afforded by CubeSats, unmanned aerial vehicles (UAVs), and smartphone technologies that are being embraced by both for-profit companies and individual researchers. Over the previous decades, space agency efforts have brought forth well-known and immensely useful satellites such as the Landsat series and the Gravity Research and Climate Experiment (GRACE) system, with costs typically of the order of 1 billion dollars per satellite and with concept-to-launch timelines of the order of 2 decades (for new missions). More recently, the proliferation of smart-phones has helped to miniaturize sensors and energy requirements, facilitating advances in the use of CubeSats that can be launched by the dozens, while providing ultra-high (3-5 m) resolution sensing of the Earth on a daily basis. Start-up companies that did not exist a decade ago now operate more satellites in orbit than any space agency, and at costs that are a mere fraction of traditional satellite missions. With these advances come new space-borne measurements, such as real-time high-definition video for tracking air pollution, storm-cell development, flood propagation, precipitation monitoring, or even for constructing digital surfaces using structure-from-motion techniques. Closer to the surface, measurements from small unmanned drones and tethered balloons have mapped snow depths, floods, and estimated evaporation at sub-metre resolutions, pushing back on spatio-temporal constraints and delivering new process insights. At ground level, precipitation has been measured using signal attenuation between antennae mounted on cell phone towers, while the proliferation of mobile devices has enabled citizen scientists to catalogue photos of environmental conditions, estimate daily average temperatures from battery state, and sense other hydrologically important variables such as channel depths using commercially available wireless devices. Global internet access is being pursued via high-altitude balloons, solar planes, and hundreds of planned satellite launches, providing a means to exploit the "internet of things" as an entirely new measurement domain. Such global access will enable real-time collection of data from billions of smartphones or from remote research platforms. This future will produce petabytes of data that can only be accessed via cloud storage and will require new analytical approaches to interpret. The extent to which today's hydrologic models can usefully ingest such massive data volumes is unclear. Nor is it clear whether this deluge of data will be usefully exploited, either because the measurements are superfluous, inconsistent, not accurate enough, or simply because we lack the capacity to process and analyse them. What is apparent is that the tools and techniques afforded by this array of novel and game-changing sensing platforms present our community with a unique opportunity to develop new insights that advance fundamental aspects of the hydrological sciences. To accomplish this will require more than just an application of the technology: in some cases, it will demand a radical rethink on how we utilize and exploit these new observing systems

Practical long-distance quantum key distribution system using decoy levels

Quantum key distribution (QKD) has the potential for widespread real-world applications. To date no secure long-distance experiment has demonstrated the truly practical operation needed to move QKD from the laboratory to the real world due largely to limitations in synchronization and poor detector performance. Here we report results obtained using a fully automated, robust QKD system based on the Bennett Brassard 1984 protocol (BB84) with low-noise superconducting nanowire single-photon detectors (SNSPDs) and decoy levels. Secret key is produced with unconditional security over a record 144.3 km of optical fibre, an increase of more than a factor of five compared to the previous record for unconditionally secure key generation in a practical QKD system.Comment: 9 page

Bilingual episodic memory: an introduction

Our current models of bilingual memory are essentially accounts of semantic memory whose goal is to explain bilingual lexical access to underlying imagistic and conceptual referents. While this research has included episodic memory, it has focused largely on recall for words, phrases, and sentences in the service of understanding the structure of semantic memory. Building on the four papers in this special issue, this article focuses on larger units of episodic memory(from quotidian events with simple narrative form to complex autobiographical memories) in service of developing a model of bilingual episodic memory. This requires integrating theory and research on how culture-specific narrative traditions inform encoding and retrieval with theory and research on the relation between(monolingual) semantic and episodic memory(Schank, 1982; Schank & Abelson, 1995; Tulving, 2002). Then, taking a cue from memory-based text processing studies in psycholinguistics(McKoon & Ratcliff, 1998), we suggest that as language forms surface in the progressive retrieval of features of an event, they trigger further forms within the same language serving to guide a within-language/ within-culture retrieval

Partial encapsulation of Pd particles by reduced ceria-zirconia

Direct observation of metal-oxide interfaces with atomic resolution can be achieved by cross-sectional high-resolution transmission electron microscopy (HRTEM). Using this approach to study the response of a model, single-crystal thin film automotive exhaust-gas catalyst, Pd particles supported on the (111) ceria-zirconia (CZO) surface, to a redox cycle, we have found two distinct processes for the partial encapsulation of the Pd particles by the reduced CZO surface that depend on their relative crystallographic orientations. In the case of the preferred orientation found for Pd particles on CZO, Pd(111)[110]//CZO(111)[110]Pd(111)[110]∕∕CZO(111)[110], a flat and sharp metal/oxide interface was maintained upon reduction, while ceria-zirconia from the adjacent surface tended to accumulate on and around the Pd particle. In rare cases, Pd particles with other orientations tended to sink into the oxide support upon reduction. Possible mechanisms for these encapsulation processes are proposed.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/87836/2/201915_1.pd