Metal oxide photoelectrodes for solar water splitting

textEfficient solar water splitting – using sunlight to produce hydrogen from water – has been an ambitious goal of the scientific community for over 40 years. At its heart this is a materials problem, with the photoelectrodes used in a photoelectrochemical cell having to satisfy all the constraints of a photovoltaic material (light absorption, charge transport) as well as being stable in water and having appropriately positioned band edges. Of the metal oxide systems studied for this purpose, we identified iron oxide (hematite, α-Fe2O3), tungsten trioxide (WO3) and an emerging (at the time) material, bismuth vanadate (BiVO4) as the most promising. In this dissertation we sought to understand and address the shortcomings of these materials, namely, carrier transport in BiVO4 and α-Fe2O3 and light absorption in WO3. We synthesized high quality single crystals of undoped and Mo and W-doped BiVO4 using the floating zone technique and carried out fundamental transport measurements. Electrons were shown to form small polarons and the Hall effect mobility was low, ~10-1 cm2 V-1 s-1 at 300 K. Critically, the mobility measured by the Hall effect may be vastly different from the drift mobility. Small-polaron hopping was found to be in the adiabatic regime and anisotropic conductivity was related to the structural arrangement of vanadium ions. Electrons are also thought to form small polarons in α-Fe2O3, but a thorough analysis had not been performed. We grew single crystals of Ti:α-Fe2O3 and characterized their electron transport to evaluate this model and probe the large anisotropy thought to occur between the basal planes. These revealed that the adiabatic small-polaron model was appropriate. Interestingly, electron transport in Ti:α-Fe2O3 was shown to be near-isotropic, contradicting the common view in the literature. Finally, we studied the effects of sulfur or iodine incorporation in WO3 with the aim to improve its visible light harvesting ability. Both of these impurities did increase visible light absorption, but performance was degraded in all cases except for very low concentrations of sulfur doping. These impurities likely form inter-gap defect bands which allow the absorption of longer wavelength light, but also degrade transport properties if present in large amounts.Chemical Engineerin

Spatial and temporal changes in seasonal range attributes in a declining barren-ground caribou herd

From 1996 to 2015 the Bathurst caribou herd has declined from approximately 349,000 to 20,000 animals. Aboriginal traditional knowledge (TK) has recently observed the later arrival of the herd below the treeline, an attribute of the autumn range. Science also predicts that seasonal range attributes (e.g., area, location) likely vary with population size, and perhaps climate. We used Aboriginal TK and science to identify several seasonal range attributes that were ex­amined for changes through time (decreasing population abundance). Attributes of seasonal ranges for female Bathurst caribou were calculated using satellite radio-collar data from January 1996 through October 2013. Climate data from CircumArctic Rangifer Monitoring and Assessment Network were analyzed for trends from 1979 to 2009. Analyses showed a significant decrease in the area of post-calving and autumn ranges, but no changes in winter and spring ranges. Results supported Aboriginal TK that female caribou have shifted the autumn range farther from the treeline and moved into the forest later in the year. Analysis of climate variables found no trends at the spatio-temporal scale of the post-calving to autumn ranges. Working hypotheses to explain these patterns, which are not mutually exclusive, include reduced predation risk, increased use of core areas at lower population density, and greater utilization of areas of taiga where arboreal and ground lichen availability and accessibility are relatively higher than in the forest. This analysis demonstrates how including Aboriginal TK can lead to stronger connections and results, with potential to provide new and different insights for further investigations

Anisotropic Small-Polaron Hopping In W:Bivo4 Single Crystals

DC electrical conductivity, Seebeck and Hall coefficients are measured between 300 and 450 K on single crystals of monoclinic bismuth vanadate that are doped n-type with 0.3% tungsten donors (W:BiVO4). Strongly activated small-polaron hopping is implied by the activation energies of the Arrhenius conductivities (about 300 meV) greatly exceeding the energies characterizing the falls of the Seebeck coefficients' magnitudes with increasing temperature (about 50 meV). Small-polaron hopping is further evidenced by the measured Hall mobility in the ab-plane (10(-1) cm(2) V-1 s(-1) at 300 K) being larger and much less strongly activated than the deduced drift mobility (about 5 x 10(-5) cm(2) V-1 s(-1) at 300 K). The conductivity and n-type Seebeck coefficient is found to be anisotropic with the conductivity larger and the Seebeck coefficient's magnitude smaller and less temperature dependent for motion within the ab-plane than that in the c-direction. These anisotropies are addressed by considering highly anisotropic next-nearest-neighbor (approximate to 5 angstrom) transfers in addition to the somewhat shorter (approximate to 4 angstrom), nearly isotropic nearest-neighbor transfers. (C) 2015 AIP Publishing LLC.U.S. Department of Energy (DOE), DE-FG02-09ER16119Welch Foundation Grant F-1436Hemphill-Gilmore Endowed FellowshipNSF MIRT DMR 1122603Chemical EngineeringTexas Materials InstituteChemistr

Warning – Taboo Words Ahead! Avoiding Attentional Capture by Spoken Taboo Distractors

We examine whether the disruption of serial short-term memory (STM) by spoken taboo distractors is due to attentional diversion and unrelated to the underlying disruptive effect of sound on serial STM more generally, which we have argued is due to order cues arising from the automatic pre-categorical processing of acoustic changes in the sound conflicting with serial–order processing within the memory task (interferenceby-process). We test whether the taboo-distractor effect is, unlike effects attributable to interference-by-process, amenable to top-down control. Experiment 1 replicated the taboo-distractor effect and showed that it is not merely a valence effect. However, promoting cognitive control by increasing focal task-load did not attenuate the effect. However, foreknowledge of the distractors did eliminate the taboo-distractor effect while having no effect on disruption by neutral words (Experiment 2). We conclude that the taboo-distractor effect results from a controllable attentional-diversion mechanism distinct from the effect of any acoustically-changing sound

Auditory Distraction During Reading: Investigating the Effects of Background Sounds on Parafoveal Processing

Previous research suggests that unexpected (deviant) sounds negatively affect reading performance by inhibiting saccadic planning, which models of reading agree takes place simultaneous to parafoveal processing. The present study examined the effect of deviant sounds on foveal and parafoveal processing. Participants read single sentences in quiet, standard (repeated sounds), or deviant sound conditions (a new sound within a repeated sound sequence). Sounds were presented with a variable delay coincident with the onset of fixations on target words during a period when saccadic programming and parafoveal processing occurred. We used the moving window paradigm (McConkie & Rayner, 1975) to manipulate the amount of information readers could extract from the parafovea (the entire sentence or a 13-character window of text). Global, sentence-level analyses showed typical disruption to reading by the window, and under quiet conditions similar effects were observed at the target and post-target word in the local analyses. Standard and deviant sounds also produced clear distraction effects of differing magnitudes at the target and post-target words, though at both regions, these effects were qualified by interactions. Effects at the target word suggested that with sounds, readers engaged in less effective parafoveal processing than under quiet. Similar patterns of effects due to standard and deviant sounds, each with a different time course, occurred at the post-target word. We conclude that distraction via auditory deviation causes disruption to parafoveal processing during reading, with such effects being modulated by the degree to which a sound’s characteristics are more or less unique

Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins

As a result of the adaptation of life to an aerobic environment, nature has evolved a panoply of metalloproteins for oxidative metabolism and protection against reactive oxygen species. Despite the diverse structures and functions of these proteins, they share common mechanistic grounds. An open-shell transition metal like iron or copper is employed to interact with O_2 and its derived intermediates such as hydrogen peroxide to afford a variety of metal–oxygen intermediates. These reactive intermediates, including metal-superoxo, -(hydro)peroxo, and high-valent metal–oxo species, are the basis for the various biological functions of O_2-utilizing metalloproteins. Collectively, these processes are called oxygen activation. Much of our understanding of the reactivity of these reactive intermediates has come from the study of heme-containing proteins and related metalloporphyrin compounds. These studies not only have deepened our understanding of various functions of heme proteins, such as O2 storage and transport, degradation of reactive oxygen species, redox signaling, and biological oxygenation, etc., but also have driven the development of bioinorganic chemistry and biomimetic catalysis. In this review, we survey the range of O_2 activation processes mediated by heme proteins and model compounds with a focus on recent progress in the characterization and reactivity of important iron–oxygen intermediates. Representative reactions initiated by these reactive intermediates as well as some context from prior decades will also be presented. We will discuss the fundamental mechanistic features of these transformations and delineate the underlying structural and electronic factors that contribute to the spectrum of reactivities that has been observed in nature as well as those that have been invented using these paradigms. Given the recent developments in biocatalysis for non-natural chemistries and the renaissance of radical chemistry in organic synthesis, we envision that new enzymatic and synthetic transformations will emerge based on the radical processes mediated by metalloproteins and their synthetic analogs

Identification, Replication, and Functional Fine-Mapping of Expression Quantitative Trait Loci in Primary Human Liver Tissue

The discovery of expression quantitative trait loci (“eQTLs”) can help to unravel genetic contributions to complex traits. We identified genetic determinants of human liver gene expression variation using two independent collections of primary tissue profiled with Agilent (n = 206) and Illumina (n = 60) expression arrays and Illumina SNP genotyping (550K), and we also incorporated data from a published study (n = 266). We found that ∼30% of SNP-expression correlations in one study failed to replicate in either of the others, even at thresholds yielding high reproducibility in simulations, and we quantified numerous factors affecting reproducibility. Our data suggest that drug exposure, clinical descriptors, and unknown factors associated with tissue ascertainment and analysis have substantial effects on gene expression and that controlling for hidden confounding variables significantly increases replication rate. Furthermore, we found that reproducible eQTL SNPs were heavily enriched near gene starts and ends, and subsequently resequenced the promoters and 3′UTRs for 14 genes and tested the identified haplotypes using luciferase assays. For three genes, significant haplotype-specific in vitro functional differences correlated directly with expression levels, suggesting that many bona fide eQTLs result from functional variants that can be mechanistically isolated in a high-throughput fashion. Finally, given our study design, we were able to discover and validate hundreds of liver eQTLs. Many of these relate directly to complex traits for which liver-specific analyses are likely to be relevant, and we identified dozens of potential connections with disease-associated loci. These included previously characterized eQTL contributors to diabetes, drug response, and lipid levels, and they suggest novel candidates such as a role for NOD2 expression in leprosy risk and C2orf43 in prostate cancer. In general, the work presented here will be valuable for future efforts to precisely identify and functionally characterize genetic contributions to a variety of complex traits

Search for dark matter produced in association with bottom or top quarks in √s = 13 TeV pp collisions with the ATLAS detector

A search for weakly interacting massive particle dark matter produced in association with bottom or top quarks is presented. Final states containing third-generation quarks and miss- ing transverse momentum are considered. The analysis uses 36.1 fb−1 of proton–proton collision data recorded by the ATLAS experiment at √s = 13 TeV in 2015 and 2016. No significant excess of events above the estimated backgrounds is observed. The results are in- terpreted in the framework of simplified models of spin-0 dark-matter mediators. For colour- neutral spin-0 mediators produced in association with top quarks and decaying into a pair of dark-matter particles, mediator masses below 50 GeV are excluded assuming a dark-matter candidate mass of 1 GeV and unitary couplings. For scalar and pseudoscalar mediators produced in association with bottom quarks, the search sets limits on the production cross- section of 300 times the predicted rate for mediators with masses between 10 and 50 GeV and assuming a dark-matter mass of 1 GeV and unitary coupling. Constraints on colour- charged scalar simplified models are also presented. Assuming a dark-matter particle mass of 35 GeV, mediator particles with mass below 1.1 TeV are excluded for couplings yielding a dark-matter relic density consistent with measurements

The ATLAS inner detector trigger performance in pp collisions at 13 TeV during LHC Run 2

The design and performance of the inner detector trigger for the high level trigger of the ATLAS experiment at the Large Hadron Collider during the 2016-18 data taking period is discussed. In 2016, 2017, and 2018 the ATLAS detector recorded 35.6 fb$^{-1}$, 46.9 fb$^{-1}$, and 60.6 fb$^{-1}$ respectively of proton-proton collision data at a centre-of-mass energy of 13 TeV. In order to deal with the very high interaction multiplicities per bunch crossing expected with the 13 TeV collisions the inner detector trigger was redesigned during the long shutdown of the Large Hadron Collider from 2013 until 2015. An overview of these developments is provided and the performance of the tracking in the trigger for the muon, electron, tau and $b$-jet signatures is discussed. The high performance of the inner detector trigger with these extreme interaction multiplicities demonstrates how the inner detector tracking continues to lie at the heart of the trigger performance and is essential in enabling the ATLAS physics programme