Hydrogen spillover on carbon-supported metal catalysts studied by inelastic neutron scattering. Surface vibrational states and hydrogen riding modes

Hydrogen spillover on carbon-supported precious metal catalysts has been investigated with inelastic neutron scattering (INS) spectroscopy. The aim, which was fully realized, was to identify spillover hydrogen on the carbon support. The inelastic neutron scattering spectra of Pt/C, Ru/C, and PtRu/C fuel cell catalysts dosed with hydrogen were determined in two sets of experiments: with the catalyst in the neutron beam and, using an annular cell, with carbon in the beam and catalyst pellets at the edge of the cell excluded from the beam. The vibrational modes observed in the INS spectra were assigned with reference to the INS of a polycyclic aromatic hydrocarbon, coronene, taken as a molecular model of a graphite layer, and with the aid of computational modeling. Two forms of spillover hydrogen were identified: H at edge sites of a graphite layer (formed after ambient dissociative chemisorption of H-2), and a weakly bound layer of mobile H atoms (formed by surface diffusion of H atoms after dissociative chernisorption of H-2 at 500 K). The INS spectra exhibited characteristic riding modes of H on carbon and on Pt or Ru. In these riding modes H atoms move in phase with vibrations of the carbon and metal lattices. The lattice modes are amplified by neutron scattering from the H atoms attached to lattice atoms. Uptake of hydrogen, and spillover, was greater for the Ru containing catalysts than for the Pt/C catalyst. The INS experiments have thus directly demonstrated H spillover to the carbon support of these metal catalysts.

Chalcogenide-halides of niobium (V). 1. Gas-phase structures of NbOBr3, NbSBr3, and NbSCl3. 2. Matrix infrared spectra and vibrational force fields of NbOBr3, NbSBr3, NbSCl3, and NbOCl3

The molecular structures of NbOBr3, NbSCl3, and NbSBr3 have been determined by gas-phase electron diffraction (GED) at nozzle-tip temperatures of 250 degreesC, taking into account the possible presence of NbOCl3 as a contaminant in the NbSCl3 sample and NbOBr3 in the NbSBr3 sample. The experimental data are consistent with trigonal-pyramidal molecules having C-3v symmetry. Infrared spectra of molecules trapped in argon or nitrogen matrices were recorded and exhibit the characteristic fundamental stretching modes for C-3v species. Well resolved isotopic fine structure (Cl-35 and Cl-37) was observed for NbSCl3, and for NbOCl3 which occurred as an impurity in the NbSCl3 spectra. Quantum mechanical calculations of the structures and vibrational frequencies of the four YNbX3 molecules (Y = O, S; X = Cl, Br) were carried out at several levels of theory, most importantly B3LYP DFT with either the Stuttgart RSC ECP or Hay-Wadt (n + 1) ECP VDZ basis set for Nb and the 6-311 G* basis set for the nonmetal atoms. Theoretical values for the bond lengths are 0.01-0.04 Angstrom longer than the experimental ones of type r(a), in accord with general experience, but the bond angles with theoretical minus experimental differences of only 1.0-1.5degrees are notably accurate. Symmetrized force fields were also calculated. The experimental bond lengths (r(g)/Angstrom) and angles (angle(alpha)/deg) with estimated 2sigma uncertainties from GED are as follows. NbOBr3: r(Nb=O) = 1.694(7), r(Nb-Br) = 2.429(2), angle(O=Nb-Br) = 107.3(5), angle(Br-Nb-Br) = 111.5(5). NbSBr3: r(Nb=S) = 2.134(10), r(Nb-Br) = 2.408(4), angle(S=Nb-Br) = 106.6(7), angle(Br-Nb-Br) = 112.2(6). NbSCl3: Nb=S) = 2.120(10), r(Nb-Cl) = 2.271(6), angle(S=Nb-Cl) = 107.8(12), angle(Cl-Nb-Cl) = 111.1(11).

Phase resetting as a mechanism of ERP generation: evidence from the power spectrum

A Neural Mass model is coupled with a novel method to generate realistic Phase reset ERPs. The power spectra of these synthetic ERPs are compared with the spectra of real ERPs and synthetic ERPs generated via the Additive model. Real ERP spectra show similarities with synthetic Phase reset ERPs and synthetic Additive ERPs.

Temporal regulation of expression of immediate early and second phase transcripts by endothelin-1 in cardiomyocytes

Background: Endothelin-1 stimulates Gq protein-coupled receptors to promote proliferation in dividing cells or hypertrophy in terminally differentiated cardiomyocytes. In cardiomyocytes, endothelin-1 rapidly (within minutes) stimulates protein kinase signaling, including extracellular-signal regulated kinases 1/2 (ERK1/2; though not ERK5), with phenotypic/physiological changes developing from approximately 12 h. Hypertrophy is associated with changes in mRNA/protein expression, presumably consequent to protein kinase signaling, but the connections between early, transient signaling events and developed hypertrophy are unknown. Results: Using microarrays, we defined the early transcriptional responses of neonatal rat cardiomyocytes to endothelin-1 over 4 h, differentiating between immediate early gene (IEG) and second phase RNAs with cycloheximide. IEGs exhibited differential temporal and transient regulation, with expression of second phase RNAs within 1 h. Of transcripts upregulated at 30 minutes encoding established proteins, 28 were inhibited >50% by U0126 (which inhibits ERK1/2/5 signaling), with 9 inhibited 25-50%. Expression of only four transcripts was not inhibited. At 1 h, most RNAs (approximately 67%) were equally changed in total and polysomal RNA with approximately 17% of transcripts increased to a greater extent in polysomes. Thus, changes in expression of most protein-coding RNAs should be reflected in protein synthesis. However, approximately 16% of transcripts were essentially excluded from the polysomes, including some protein-coding mRNAs, presumably inefficiently translated. Conclusion: The phasic, temporal regulation of early transcriptional responses induced by endothelin-1 in cardiomyocytes indicates that, even in terminally differentiated cells, signals are propagated beyond the primary signaling pathways through transcriptional networks leading to phenotypic changes (that is, hypertrophy). Furthermore, ERK1/2 signaling plays a major role in this response.

The relationship between El Niño and the western North Pacific summer climate in a coupled GCM: role of the transition of El Niño decaying phases

This study investigates the impacts of the transition of El Niño decaying phases on the western North Pacific anticyclone (WNPAC) anomalies in the subsequent summer with a coupled GCM. The modeling results suggest that the El Niños with short decaying phases lead to significant WNPAC anomalies in the following summer, which are contributed to mainly by the El Niños followed by La Niñas, in comparison with those not followed by La Niñas. In contrast, the long decaying cases are associated with the disappearance of WNPAC anomalies in the summer. These differences in the WNP circulation anomalies can be explained by the different configurations of simultaneous SSTs in the Indian Ocean and in the central and eastern tropical Pacific: positive SSTs in the former region and negative ones in the latter region constructively induce significant WNPAC anomalies for the short decaying cases, while the roles of positive SSTs in both regions for the long decaying cases work destructively and lead to weak WNP circulation anomalies. Further analysis indicates that the different lengths of El Niño decaying phases are predicted by the strength of Indian Ocean SSTs in the mature winter. The warmer wintertime Indian Ocean SSTs favor the anomalous easterly wind over the western and central equatorial Pacific in the subsequent summer, leading to a short decaying of El Niño. Thus, the strength of wintertime Indian Ocean SSTs is one of the important factors that affect the length of El Niño decaying phase and resultant WNPAC anomalies in the following summer.

SANS/WANS time-resolving neutron scattering studies of polymer phase transitions using NIMROD

We use new neutron scattering instrumentation to follow in a single quantitative time-resolving experiment, the three key scales of structural development which accompany the crystallisation of synthetic polymers. These length scales span 3 orders of magnitude of the scattering vector. The study of polymer crystallisation dates back to the pioneering experiments of Keller and others who discovered the chain-folded nature of the thin lamellae crystals which are normally found in synthetic polymers. The inherent connectivity of polymers makes their crystallisation a multiscale transformation. Much understanding has developed over the intervening fifty years but the process has remained something of a mystery. There are three key length scales. The chain folded lamellar thickness is ~ 10nm, the crystal unit cell is ~ 1nm and the detail of the chain conformation is ~ 0.1nm. In previous work these length scales have been addressed using different instrumention or were coupled using compromised geometries. More recently researchers have attempted to exploit coupled time-resolved small-angle and wide-angle x-ray experiments. These turned out to be challenging experiments much related to the challenge of placing the scattering intensity on an absolute scale. However, they did stimulate the possibility of new phenomena in the very early stages of crystallisation. Although there is now considerable doubt on such experiments, they drew attention to the basic question as to the process of crystallisation in long chain molecules. We have used NIMROD on the second target station at ISIS to follow all three length scales in a time-resolving manner for poly(e-caprolactone). The technique can provide a single set of data from 0.01 to 100Å-1 on the same vertical scale. We present the results using a multiple scale model of the crystallisation process in polymers to analyse the results.

Tropical Atlantic variability modes (1979–2002). Part I: Time-evolving SST modes related to West African rainfall

This work presents a description of the 1979–2002 tropical Atlantic (TA) SST variability modes coupled to the anomalous West African (WA) rainfall during the monsoon season. The time-evolving SST patterns, with an impact on WA rainfall variability, are analyzed using a new methodology based on maximum covariance analysis. The enhanced Climate Prediction Center (CPC) Merged Analysis of Precipitation (CMAP) dataset, which includes measures over the ocean, gives a complete picture of the interannual WA rainfall patterns for the Sahel dry period. The leading TA SST pattern, related to the Atlantic El Niño, is coupled to anomalous precipitation over the coast of the Gulf of Guinea, which corresponds to the second WA rainfall principal component. The thermodynamics and dynamics involved in the generation, development, and damping of this mode are studied and compared with previous works. The SST mode starts at the Angola/Benguela region and is caused by alongshore wind anomalies. It then propagates westward via Rossby waves and damps because of latent heat flux anomalies and Kelvin wave eastward propagation from an off-equatorial forcing. The second SST mode includes the Mediterranean and the Atlantic Ocean, showing how the Mediterranean SST anomalies are those that are directly associated with the Sahelian rainfall. The global signature of the TA SST patterns is analyzed, adding new insights about the Pacific– Atlantic link in relation to WA rainfall during this period. Also, this global picture suggests that the Mediterranean SST anomalies are a fingerprint of large-scale forcing. This work updates the results given by other authors, whose studies are based on different datasets dating back to the 1950s, including both the wet and the dry Sahel periods.

Coupled Kelvin-wave and mirage-wave instabilities in semigeostrophic dynamics

A weak instability mode, associated with phase-locked counterpropagating coastal Kelvin waves in horizontal anticyclonic shear, is found in the semigeostrophic (SG) equations for stratified flow in a channel. This SG instability mode approximates a similar mode found in the Euler equations in the limit in which particle-trajectory slopes are much smaller than f/N, where f is the Coriolis frequency and N > f the buoyancy frequency. Though weak under normal parameter conditions, this instability mode is of theoretical interest because its existence accounts for the failure of an Arnol’d-type stability theorem for the SG equations. In the opposite limit, in which the particle motion is purely vertical, the Euler equations allow only buoyancy oscillations with no horizontal coupling. The SG equations, on the other hand, allow a physically spurious coastal “mirage wave,” so called because its velocity field vanishes despite a nonvanishing disturbance pressure field. Counterpropagating pairs of these waves can phase-lock to form a spurious “mirage-wave instability.” Closer examination shows that the mirage wave arises from failure of the SG approximations to be self-consistent for trajectory slopes f/N.

Analysis of precipitation climatology simulated by high resolution coupled global models over the South America

The results of coupled high resolution global models (CGCMs) over South America are discussed. HiGEM1.2 and HadGEM1.2 simulations, with horizontal resolution of ~90 and 135 km, respectively, are compared. Precipitation estimations from CMAP (Climate Prediction Center—Merged Analysis of Precipitation), CPC (Climate Prediction Center) and GPCP (Global Precipitation Climatology Project) are used for validation. HiGEM1.2 and HadGEM1.2 simulated seasonal mean precipitation spatial patterns similar to the CMAP. The positioning and migration of the Intertropical Convergence Zone and of the Pacific and Atlantic subtropical highs are correctly simulated by the models. In HiGEM1.2 and HadGEM1.2, the intensity and locations of the South Atlantic Convergence Zone are in agreement with the observed dataset. The simulated annual cycles are in phase with estimations of rainfall for most of the six regions considered. An important result is that HiGEM1.2 and HadGEM1.2 eliminate a common problem of coarse resolution CGCMs, which is the simulation of a semiannual cycle of precipitation due to the semiannual solar forcing. Comparatively, the use of high resolution in HiGEM1.2 reduces the dry biases in the central part of Brazil during austral winter and spring and in most part of the year over an oceanic box in eastern Uruguay.

Evaluation of coupled ocean-atmosphere simulations of northern hemisphere extratropical climates in the mid-Holocene

We have used the BIOME4 biogeography–biochemistry model and comparison with palaeovegetation data to evaluate the response of six ocean–atmosphere general circulation models to mid-Holocene changes in orbital forcing in the mid- to high-latitudes of the northern hemisphere. All the models produce: (a) a northward shift of the northern limit of boreal forest, in response to simulated summer warming in high-latitudes. The northward shift is markedly asymmetric, with larger shifts in Eurasia than in North America; (b) an expansion of xerophytic vegetation in mid-continental North America and Eurasia, in response to increased temperatures during the growing season; (c) a northward expansion of temperate forests in eastern North America, in response to simulated winter warming. The northward shift of the northern limit of boreal forest and the northward expansion of temperate forests in North America are supported by palaeovegetation data. The expansion of xerophytic vegetation in mid-continental North America is consistent with palaeodata, although the extent may be over-estimated. The simulated expansion of xerophytic vegetation in Eurasia is not supported by the data. Analysis of an asynchronous coupling of one model to an equilibrium-vegetation model suggests vegetation feedback exacerbates this mid-continental drying and produces conditions more unlike the observations. Not all features of the simulations are robust: some models produce winter warming over Europe while others produce winter cooling. As a result, some models show a northward shift of temperate forests (consistent with, though less marked than, the expansion shown by data) and others produce a reduction in temperate forests. Elucidation of the cause of such differences is a focus of the current phase of the Palaeoclimate Modelling Intercomparison Project.

Results of PMIP2 coupled simulations of the mid-Holocene and Last Glacial Maximum, Part 2: feedbacks with emphasis on the location of the ITCZ and mid- and high latitudes heat budget

A set of coupled ocean-atmosphere(-vegetation) simulations using state of the art climate models is now available for the Last Glacial Maximum (LGM) and the Mid-Holocene (MH) through the second phase of the Paleoclimate Modeling Intercomparison Project (PMIP2). Here we quantify the latitudinal shift of the location of the Intertropical Convergence Zone (ITCZ) in the tropical regions during boreal summer and the change in precipitation in the northern part of the ITCZ. For both periods the shift is more pronounced over the continents and East Asia. The maritime continent is the region where the largest spread is found between models. We also clearly establish that the larger the increase in the meridional temperature gradient in the tropical Atlantic during summer at the MH, the larger the change in precipitation over West Africa. The vegetation feedback is however not as large as found in previous studies, probably due to model differences in the control simulation. Finally, we show that the feedback from snow and sea-ice at mid and high latitudes contributes for half of the cooling in the Northern Hemisphere for the LGM, with the remaining being achieved by the reduced CO2 and water vapour in the atmosphere. For the MH the snow and albedo feedbacks strengthen the spring cooling and enhance the boreal summer warming, whereas water vapour reinforces the late summer warming. These feedbacks are modest in the Southern Hemisphere. For the LGM most of the surface cooling is due to CO2 and water vapour.

Results of PMIP2 coupled simulations of the mid-Holocene and Last Glacial Maximum, Part 1: experiments and large-scale features

A set of coupled ocean-atmosphere simulations using state of the art climate models is now available for the Last Glacial Maximum and the Mid-Holocene through the second phase of the Paleoclimate Modeling Intercomparison Project (PMIP2). This study presents the large-scale features of the simulated climates and compares the new model results to those of the atmospheric models from the first phase of the PMIP, for which sea surface temperature was prescribed or computed using simple slab ocean formulations. We consider the large-scale features of the climate change, pointing out some of the major differences between the different sets of experiments. We show in particular that systematic differences between PMIP1 and PMIP2 simulations are due to the interactive ocean, such as the amplification of the African monsoon at the Mid-Holocene or the change in precipitation in mid-latitudes at the LGM. Also the PMIP2 simulations are in general in better agreement with data than PMIP1 simulations.

Magnetic resonant modes in a wireless-powered circuit

A pair of circular loops of the same radius set at a distance form a closed induction circuit. Coupled to a capacitor, these loops form a resonant circuit wherein energy is transported from one to the other. When a current is introduced into one of the loops, it is received by its companion. This is due to the propagation of magnetic waves through the medium, in this instance, atmospheric air of a characteristic impedance.

Coupled versus uncoupled hindcast simulations of the Madden-Julian oscillation in the Year of Tropical Convection

This study investigates the impact of a full interactive ocean on daily initialised 15 day hindcasts of the Madden-Julian oscillation (MJO), measured against a Met Office Unified Model (MetUM) atmosphere control simulation (AGCM) during a 3 month period of the Year of Tropical Convection (YOTC). Results indicated that the coupled configuration (CGCM) extends MJO predictability over that of the AGCM, by up to 3-5 days. Propagation is improved in the CGCM, which we partly attribute to a more realistic phase relationship between sea surface temperature (SST) and convection. In addition, the CGCM demonstrates skill in representing downwelling oceanic Kelvin and Rossby waves which warm SSTs along their trajectory, with the potential to feed back on the atmosphere. These results imply that an ocean model capable of simulating internal ocean waves may be required to capture the full effect of air-sea coupling for the MJO.

The Met Office Global Coupled model 2.0 (GC2) configuration

The latest coupled configuration of the Met Office Unified Model (Global Coupled configuration 2, GC2) is presented. This paper documents the model components which make up the configuration (although the scientific description of these components is detailed elsewhere) and provides a description of the coupling between the components. The performance of GC2 in terms of its systematic errors is assessed using a variety of diagnostic techniques. The configuration is intended to be used by the Met Office and collaborating institutes across a range of timescales, with the seasonal forecast system (GloSea5) and climate projection system (HadGEM) being the initial users. In this paper GC2 is compared against the model currently used operationally in those two systems. Overall GC2 is shown to be an improvement on the configurations used currently, particularly in terms of modes of variability (e.g. mid-latitude and tropical cyclone intensities, the Madden–Julian Oscillation and El Niño Southern Oscillation). A number of outstanding errors are identified with the most significant being a considerable warm bias over the Southern Ocean and a dry precipitation bias in the Indian and West African summer monsoons. Research to address these is ongoing.