Fine tuning the ionic liquid–vacuum outer atomic surface using ion mixtures

Ionic liquid–vacuum outer atomic surfaces can be created that are remarkably different from the bulk composition. In this communication we demonstrate, using low-energy ion scattering (LEIS), that for ionic liquid mixtures the outer atomic surface shows significantly more atoms from anions with weaker cation–anion interactions (and vice versa)

Molecular elucidation of CO2 methanation over a highly active, selective and stable LaNiO3/CeO2-derived catalyst by in situ FTIR and NAP-XPS

The CO2 methanation mechanism over the highly active (TOF=75.1 h−1), selective (>92%) and stable 10% LaNiO3/CeO2-derived catalyst is still unresolved. The surface of the catalyst is monitored under hydrogenation (H2), oxidizing (CO2) and CO2 methanation (H2 +CO2) conditions by near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) using synchrotron radiation. Meanwhile, the main reaction intermediates are identified by in situ FTIR analysis. NAP-XPS experiments confirm that LaNiO3 perovskite reduction leads to the ex-solution of Ni0 nanoparticles and Ni2+single bondCeO2−x and Ni2+single bondLa2O3 interfaces conformation, favouring the CO2 adsorption and the H2 dissociation/transfer. In situ FTIR experiments combined with the C1s spectra (NAP-XPS) suggest that the CO2 activation occurs on CeO2−x (oxygen vacancies and OH–) at low temperatures, in the form of bicarbonates; whereas, mono-/bidentate carbonates are formed on different strength La2O3 sites at increasing temperatures. These species are consecutively reduced to formates, as the main reaction intermediate, and methane by the H spilled from Ni0 nanoparticles near to NiOsingle bondCeO2−x and NiOsingle bondLa2O3 interfaces.Support for this study was provided by Projects PID2019–105960RB-C21 and PID2019–105960RB-C22 by MCIN/AEI/10.13039/501100011033, the Basque Government (Project IT1509–2022), Generalitat Valenciana (CIPROM/2021/74) and ALBA synchrotron. One of the authors (JAOC) acknowledges the postdoctoral research grant (DOCREC20/49) provided by the University of the Basque Country (UPV/EHU)

Correcting flaws in the assignment of nitrogen chemical environments in N-doped graphene

X-ray Photoelectron Spectroscopy (XPS) applied to N-doped graphene leads to a rather broad N(1s) core level signal that, based on different sources available in the literature, is most often interpreted by fitting the experimental spectra to three peaks. The resulting N(1s) features are assigned to graphitic, pyrrolic, and pyridinic nitrogen, even if these are far from being uniquely defined in the literature. This broadly accepted interpretation has been questioned by recent accurate Hartree-Fock calculations concluding that graphitic and pyrrolic N(1s) core level binding energies are too close to be distinguished. Consideration of models with N in other so far unexplored environments such as N dimers or N at defects show some variations in the calculated core level binding energies. However, these are not large enough to justify a third peak and suggest that the usual three peaks interpretation of the N(1s) XPS in N-doped graphene may be an artefact caused by the fitting procedure. New measurements have been carried out for samples of N-doped graphene and the obtained N(1s) spectra fitted to two or three peaks. It turns out that the spectra can be equally fitted using two or three peaks but only the former is consistent with the results of the unbiased ab initio calculations which calls for a revision of the usual assignment

Enabling water-based processing of graphene/alumina composites using an infiltration approach with amphiphilic triblock copolymers

Enabling the direct infiltration of freeze-cast graphene structures with water-based ceramic suspensions, otherwise prevented by graphene’s intrinsic hydrophobic behaviour, can lead to the production of hierarchical graphene/ceramic composites in a cost-effective and replicable manner. In this study, the addition of a triblock copolymer (PF127) in the formulation of water-based alumina slurries was used to allow the integration with reduced graphene oxide (rGO) scaffolds combining freeze-casting, wet chemistry processing and Spark Plasma Sintering. Wettability and infiltration tests were performed to optimise the composition of the ceramic suspension, leading to the preservation of alignment in embedded rGO scaffolds and maintaining channel widths of 5–15▒μm upon sintering at 1500∘ C

Monitoring by in situ NAP-XPS of active sites for CO2 methanation on a Ni/CeO2 catalyst

Ni/CeO2 catalysts are very active and selective for total hydrogenation of CO2 to methane, but the nature of the active sites is still unclear. The surface of a Ni/CeO2 catalyst has been monitored under CO2 methanation conditions by Near Ambient Pressure-XPS (NAP-XPS) using synchrotron radiation, and has been concluded that the species involved in the redox processes taking place during the CO2 methanation mechanism are the Ni2+-CeO2/Ni0 and Ce4+/Ce3+ pairs. In addition, a small fraction of nickel is present on the catalyst surface forming NiO and Ni2+-carbonates/hydroxyls (around 20% of the total surface nickel), but these species do not participate in the redox processes of the methanation mechanism. Under CO2 methanation conditions the H2 reduction rate of the Ni2+-CeO2/Ni0 and Ce4+/Ce3+ couples is much faster than their CO2 reoxidation rate (2 times faster, at least, at 300ºC), but a certain proportion of nickel always remains oxidized under reaction conditions. The high activity of Ni/CeO2 catalysts for CO2 methanation is tentatively attributed to the simultaneous presence of Ni2+-CeO2 and Ni0 active sites where CO2 and H2 are expected to be efficiently dissociated, respectively.Generalitat Valenciana, Spain (PROMETEO/2018/0765) Ministry for Science and Innovation MICINN, Spain (Projects PID2019-105960RB-C21 and PID2019-105960RB-C22) Junta de Andalucía, Spain (Project P18-RTJ-2974); European Union’s Horizon 2020 Research and Innovation Program (Marie Skłodowska-Curie grant agreement No 713567) Science Foundation Ireland Research Centre, Ireland (award 12/RC/2278_P2) ALBA synchrotron, Spain (Proposal number: ID 2020094556)

Captured by Evil: The Idea of Corruption in Law

Corruption is one of the most powerful words in the English language. When it comes to the treatment of corruption by law, however, corruption is a troubled concept. With increasing recognition of the costs of corruption for economic development, democratic governance, international aid programs, and other world goals, attempts to articulate what this destructive force is have led to an avalanche of theoretical writing. In the last fifteen years, corruption has been variously defined as the violation of law, a public servant\u27s breach of public duty, an agent\u27s betrayal of a principal\u27s interests, the pursuit of secrecy, the denial of equality in political influence, and other ways. In the end, however, all of these efforts fall short. Corruption is more than law-breaking: it is more than breaching public duties. To say that A is a thief or that A has breached his duty is not to say that A is corrupt. The latter is far more powerful, far more emotional, far more essential than the others. It is more than secrecy, or the denial of equal opportunity. It is a searing indictment, somehow, not only of A\u27s act but of A\u27s character. It is a statement not only of what A has done, but of what A has become. Corruption is, I argue, a far more powerful idea than these existing legal understandings have articulated: it is the idea of capture by evil, the possession of the individual by evil, in law. Just as we once believed in corruption of the blood in American law, which decreed that offspring of those who had committed crimes were believed to be irrevocably tainted by their parents\u27 depravity, so we still retain - through the idea of corruption - the belief that individual evil extends beyond acts of wrongdoing, or the denial of equal opportunity, or breach of the public trust. It is this idea of corruption, I argue - the idea of capture by evil - that, although unarticulated, drives our understandings of corruption in law. It drives our understanding of corrupt judges, who, once corrupt, we believe will act so in every case. It drives our understanding of campaign finance reform, where we fear deep corruption of the process from the occurrence of corrupt acts. It drives our understanding of corruption as a systemic effect and systemic influence, which presents institutional dangers that are greater than other crimes, and that requires purgation rather than simple law enforcement. This Article explores this deeper understanding of corruption, its impacts in areas such as judicial corruption and campaign finance reform, and its implications for the principle of the rule of law

Clonal chromosomal mosaicism and loss of chromosome Y in elderly men increase vulnerability for SARS-CoV-2

The pandemic caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2, COVID-19) had an estimated overall case fatality ratio of 1.38% (pre-vaccination), being 53% higher in males and increasing exponentially with age. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, we found 133 cases (1.42%) with detectable clonal mosaicism for chromosome alterations (mCA) and 226 males (5.08%) with acquired loss of chromosome Y (LOY). Individuals with clonal mosaic events (mCA and/or LOY) showed a 54% increase in the risk of COVID-19 lethality. LOY is associated with transcriptomic biomarkers of immune dysfunction, pro-coagulation activity and cardiovascular risk. Interferon-induced genes involved in the initial immune response to SARS-CoV-2 are also down-regulated in LOY. Thus, mCA and LOY underlie at least part of the sex-biased severity and mortality of COVID-19 in aging patients. Given its potential therapeutic and prognostic relevance, evaluation of clonal mosaicism should be implemented as biomarker of COVID-19 severity in elderly people. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, individuals with clonal mosaic events (clonal mosaicism for chromosome alterations and/or loss of chromosome Y) showed an increased risk of COVID-19 lethality

Global maps of soil temperature

Research in global change ecology relies heavily on global climatic grids derived from estimates of air temperature in open areas at around 2 m above the ground. These climatic grids do not reflect conditions below vegetation canopies and near the ground surface, where critical ecosystem functions occur and most terrestrial species reside. Here, we provide global maps of soil temperature and bioclimatic variables at a 1-km² resolution for 0–5 and 5–15 cm soil depth. These maps were created by calculating the difference (i.e., offset) between in-situ soil temperature measurements, based on time series from over 1200 1-km² pixels (summarized from 8500 unique temperature sensors) across all the world’s major terrestrial biomes, and coarse-grained air temperature estimates from ERA5-Land (an atmospheric reanalysis by the European Centre for Medium-Range Weather Forecasts). We show that mean annual soil temperature differs markedly from the corresponding gridded air temperature, by up to 10°C (mean = 3.0 ± 2.1°C), with substantial variation across biomes and seasons. Over the year, soils in cold and/or dry biomes are substantially warmer (+3.6 ± 2.3°C) than gridded air temperature, whereas soils in warm and humid environments are on average slightly cooler (-0.7 ± 2.3°C). The observed substantial and biome-specific offsets emphasize that the projected impacts of climate and climate change on near-surface biodiversity and ecosystem functioning are inaccurately assessed when air rather than soil temperature is used, especially in cold environments. The global soil-related bioclimatic variables provided here are an important step forward for any application in ecology and related disciplines. Nevertheless, we highlight the need to fill remaining geographic gaps by collecting more in-situ measurements of microclimate conditions to further enhance the spatiotemporal resolution of global soil temperature products for ecological applications

Global maps of soil temperature.

Research in global change ecology relies heavily on global climatic grids derived from estimates of air temperature in open areas at around 2 m above the ground. These climatic grids do not reflect conditions below vegetation canopies and near the ground surface, where critical ecosystem functions occur and most terrestrial species reside. Here, we provide global maps of soil temperature and bioclimatic variables at a 1-km2 resolution for 0-5 and 5-15 cm soil depth. These maps were created by calculating the difference (i.e. offset) between in situ soil temperature measurements, based on time series from over 1200 1-km2 pixels (summarized from 8519 unique temperature sensors) across all the world's major terrestrial biomes, and coarse-grained air temperature estimates from ERA5-Land (an atmospheric reanalysis by the European Centre for Medium-Range Weather Forecasts). We show that mean annual soil temperature differs markedly from the corresponding gridded air temperature, by up to 10°C (mean = 3.0 ± 2.1°C), with substantial variation across biomes and seasons. Over the year, soils in cold and/or dry biomes are substantially warmer (+3.6 ± 2.3°C) than gridded air temperature, whereas soils in warm and humid environments are on average slightly cooler (-0.7 ± 2.3°C). The observed substantial and biome-specific offsets emphasize that the projected impacts of climate and climate change on near-surface biodiversity and ecosystem functioning are inaccurately assessed when air rather than soil temperature is used, especially in cold environments. The global soil-related bioclimatic variables provided here are an important step forward for any application in ecology and related disciplines. Nevertheless, we highlight the need to fill remaining geographic gaps by collecting more in situ measurements of microclimate conditions to further enhance the spatiotemporal resolution of global soil temperature products for ecological applications