Enhanced Carrier Transport and Bandgap Reduction in Sulfur Modified BiVO4 Photoanodes

Recent progress on bismuth vanadate BiVO4 has shown it to be among the highest performing metal oxide photoanode materials. However, further improvement, especially in the form of thin film photoelectrodes, is hampered by its poor charge carrier transport and its relatively wide bandgap. Here, sulfur incorporation is used to address these limitations. A maximum bandgap decrease of 0.3 eV is obtained, which increases the theoretical maximum solar to hydrogen efficiency from 9 to 12 . Hard X ray photoelectron spectroscopy HAXPES measurements as well as density functional theory DFT calculations show that the main reason for the bandgap decrease is an upward shift of the valence band maximum. Time resolved microwave conductivity measurements reveal an 3 times higher charge carrier mobility compared to unmodified BiVO4, resulting in a 70 increase in the carrier diffusion length. This work demonstrates that sulfur doping can be a promising and practical method to improve the performance of wide bandgap metal oxide photoelectrode

Interfacial Oxide Formation Limits the Photovoltage of Alpha SnWO4 NiOx Photoanodes Prepared by Pulsed Laser Deposition

alpha SnWO4 is a promising metal oxide photoanode material for direct photoelectrochemical water splitting. With a band gap of 1.9 eV, it ideally matches the requirements as a top absorber in a tandem device theoretically capable of achieving solar to hydrogen STH efficiencies above 20 . It suffers from photoelectrochemical instability, but NiOx protection layers have been shown to help overcome this limitation. At the same time, however, such protection layers seem to reduce the photovoltage that can be generated at the solid electrolyte junction. In this study, an extensive analysis of the alpha SnWO4 NiOx interface is performed by synchrotron based hard X ray photoelectron spectroscopy HAXPES . NiOx deposition introduces a favorable upwards band bending, but also oxidizes Sn2 to Sn4 at the interface. By combining the HAXPES data with open circuit potential OCP analysis, density functional theory DFT calculations, and Monte Carlo based photoemission spectra simulation using SESSA, the presence of a thin oxide layer at the alpha SnWO4 NiOx interface is suggested and shown to be responsible for the limited photovoltage. Based on this new found understanding, suitable mitigation strategies can be proposed. Overall, this study demonstrates the complex nature of solid state interfaces in multi layer photoelectrodes, which needs to be unraveled to design efficient heterostructured photoelectrodes for solar water splittin

Nature of Nitrogen Incorporation in BiVO4 Photoanodes through Chemical and Physical Methods

In recent years, BiVO4 has been optimized as a photoanode material to produce photocurrent densities close to its theoretical maximum under AM1.5 solar illumination. Its performance is, therefore, limited by its 2.4 amp; 8201;eV bandgap. Herein, nitrogen is incorporated into BiVO4 to shift the valence band position to higher energies and thereby decreases the bandgap. Two different approaches are investigated modification of the precursors for the spray pyrolysis recipe and post amp; 8208;deposition nitrogen ion implantation. Both methods result in a slight red shift of the BiVO4 bandgap and optical absorption onset. Although previous reports on N amp; 8208;modified BiVO4 assumed individual nitrogen atoms to substitute for oxygen, X amp; 8208;ray photoelectron spectroscopy on the samples reveals the presence of molecular nitrogen i.e., N2 . Density functional theory calculations confirm the thermodynamic stability of the incorporation and reveal that N2 coordinates to two vanadium atoms in a bridging configuration. Unfortunately, nitrogen incorporation also results in the formation of a localized state of amp; 8776;0.1 amp; 8201;eV below the conduction band minimum of BiVO4, which suppresses the photoactivity at longer wavelengths. These findings provide important new insights on the nature of nitrogen incorporation into BiVO4 and illustrate the need to find alternative lower amp; 8208;bandgap absorber materials for photoelectrochemical energy conversion application

Search for heavy gauge W ′ bosons in events with an energetic lepton and large missing transverse momentum at √s = 13 TeV

A search is presented for W′ bosons in events with an electron or muon and large missing transverse momentum, using proton–proton collision data at √s=13 TeV collected with the CMS detector in 2015 and corresponding to an integrated luminosity of 2.3 fb−1. No evidence of an excess of events relative to the standard model expectations is observed. For a W′ boson described by the sequential standard model, upper limits at 95% confidence level are set on the product of the production cross section and branching fraction and lower limits are established on the new boson mass. Masses below 4.1 TeV are excluded combining electron and muon decay channels, significantly improving upon the results obtained with the 8 TeV data. Exclusion limits at 95% confidence level on the product of the W′ production cross section and branching fraction are also derived in combination with the 8 TeV data. Finally, exclusion limits are set for the production of generic W′ bosons decaying into this final state using a model-independent approach

Global, regional, and national under-5 mortality, adult mortality, age-specific mortality, and life expectancy, 1970-2016: A systematic analysis for the Global Burden of Disease Study 2016

Background: Detailed assessments of mortality patterns, particularly age-specific mortality, represent a crucial input that enables health systems to target interventions to specific populations. Understanding how all-cause mortality has changed with respect to development status can identify exemplars for best practice. To accomplish this, the Global Burden of Diseases, Injuries, and Risk Factors Study 2016 (GBD 2016) estimated age-specific and sex-specific all-cause mortality between 1970 and 2016 for 195 countries and territories and at the subnational level for the five countries with a population greater than 200 million in 2016. Methods: We have evaluated how well civil registration systems captured deaths using a set of demographic methods called death distribution methods for adults and from consideration of survey and census data for children younger than 5 years. We generated an overall assessment of completeness of registration of deaths by dividing registered deaths in each location-year by our estimate of all-age deaths generated from our overall estimation process. For 163 locations, including subnational units in countries with a population greater than 200 million with complete vital registration (VR) systems, our estimates were largely driven by the observed data, with corrections for small fluctuations in numbers and estimation for recent years where there were lags in data reporting (lags were variable by location, generally between 1 year and 6 years). For other locations, we took advantage of different data sources available to measure under-5 mortality rates (U5MR) using complete birth histories, summary birth histories, and incomplete VR with adjustments; we measured adult mortality rate (the probability of death in individuals aged 15-60 years) using adjusted incomplete VR, sibling histories, and household death recall. We used the U5MR and adult mortality rate, together with crude death rate due to HIV in the GBD model life table system, to estimate age-specific and sex-specific death rates for each location-year. Using various international databases, we identified fatal discontinuities, which we defined as increases in the death rate of more than one death per million, resulting from conflict and terrorism, natural disasters, major transport or technological accidents, and a subset of epidemic infectious diseases; these were added to estimates in the relevant years. In 47 countries with an identified peak adult prevalence for HIV/AIDS of more than 0.5% and where VR systems were less than 65% complete, we informed our estimates of age-sex-specific mortality using the Estimation and Projection Package (EPP)-Spectrum model fitted to national HIV/AIDS prevalence surveys and antenatal clinic serosurveillance systems. We estimated stillbirths, early neonatal, late neonatal, and childhood mortality using both survey and VR data in spatiotemporal Gaussian process regression models. We estimated abridged life tables for all location-years using age-specific death rates. We grouped locations into development quintiles based on the Socio-demographic Index (SDI) and analysed mortality trends by quintile. Using spline regression, we estimated the expected mortality rate for each age-sex group as a function of SDI. We identified countries with higher life expectancy than expected by comparing observed life expectancy to anticipated life expectancy on the basis of development status alone. Findings: Completeness in the registration of deaths increased from 28% in 1970 to a peak of 45% in 2013; completeness was lower after 2013 because of lags in reporting. Total deaths in children younger than 5 years decreased from 1970 to 2016, and slower decreases occurred at ages 5-24 years. By contrast, numbers of adult deaths increased in each 5-year age bracket above the age of 25 years. The distribution of annualised rates of change in age-specific mortality rate differed over the period 2000 to 2016 compared with earlier decades: increasing annualised rates of change were less frequent, although rising annualised rates of change still occurred in some locations, particularly for adolescent and younger adult age groups. Rates of stillbirths and under-5 mortality both decreased globally from 1970. Evidence for global convergence of death rates was mixed; although the absolute difference between age-standardised death rates narrowed between countries at the lowest and highest levels of SDI, the ratio of these death rates - a measure of relative inequality - increased slightly. There was a strong shift between 1970 and 2016 toward higher life expectancy, most noticeably at higher levels of SDI. Among countries with populations greater than 1 million in 2016, life expectancy at birth was highest for women in Japan, at 86.9 years (95% UI 86.7-87.2), and for men in Singapore, at 81.3 years (78.8-83.7) in 2016. Male life expectancy was generally lower than female life expectancy between 1970 and 2016, and the gap between male and female life expectancy increased with progression to higher levels of SDI. Some countries with exceptional health performance in 1990 in terms of the difference in observed to expected life expectancy at birth had slower progress on the same measure in 2016. Interpretation Globally, mortality rates have decreased across all age groups over the past five decades, with the largest improvements occurring among children younger than 5 years. However, at the national level, considerable heterogeneity remains in terms of both level and rate of changes in age-specific mortality; increases in mortality for certain age groups occurred in some locations. We found evidence that the absolute gap between countries in age-specific death rates has declined, although the relative gap for some age-sex groups increased. Countries that now lead in terms of having higher observed life expectancy than that expected on the basis of development alone, or locations that have either increased this advantage or rapidly decreased the deficit from expected levels, could provide insight into the means to accelerate progress in nations where progress has stalled. Copyright © The Author(s)