Revealing the active phase of copper during the electroreduction of CO2 in aqueous electrolyte by correlating in situ x-ray spectroscopy and in situ electron microscopy

The variation in the morphology and electronic structure of copper during the electroreduction of CO2 into valuable hydrocarbons and alcohols was revealed by combining in situ surface- and bulk-sensitive X-ray spectroscopies with electrochemical scanning electron microscopy. These experiments proved that the electrified interface surface and near-surface are dominated by reduced copper. The selectivity to the formation of the key C–C bond is enhanced at higher cathodic potentials as a consequence of increased copper metallicity. In addition, the reduction of the copper oxide electrode and oxygen loss in the lattice reconstructs the electrode to yield a rougher surface with more uncoordinated sites, which controls the dissociation barrier of water and CO2. Thus, according to these results, copper oxide species can only be stabilized kinetically under CO2 reduction reaction conditions

Liquid State Anomalies for the Stell-Hemmer Core-Softened Potential

We study the Stell-Hemmer potential using both analytic (exact $1d$ and approximate $2d$) solutions and numerical $2d$ simulations. We observe in the liquid phase an anomalous decrease in specific volume and isothermal compressibility upon heating, and an anomalous increase in the diffusion coefficient with pressure. We relate the anomalies to the existence of two different local structures in the liquid phase. Our results are consistent with the possibility of a low temperature/high pressure liquid-liquid phase transition.Comment: 4 pages in one gzipped ps file including 11 figures; One RevTex and 11 gzipped eps figure

On the activity/selectivity and phase stability of thermally grown copper oxides during the electrocatalytic reduction of CO2

Revealing the active nature of oxide-derived copper is of key importance to understand its remarkable catalytic performance during the cathodic CO2 reduction reaction (CO2RR) to produce valuable hydrocarbons. Using advanced spectroscopy, electron microscopy, and electrochemically active surface area characterization techniques, the electronic structure and the changes in the morphology/roughness of thermally oxidized copper thin films were revealed during CO2RR. For this purpose, we developed an in situ cell for X-ray spectroscopy that could be operated accurately in the presence of gases or liquids to clarify the role of the initial thermal oxide phase and its active phase during the electrocatalytic reduction of CO2. It was found that the Cu(I) species formed during the thermal treatment are readily reduced to Cu0 during the CO2RR, whereas Cu(II) species are hardly reduced. In addition, Cu(II) oxide electrode dissolution was found to yield a porous/void structure, where the lack of electrical connection between isolated islands prohibits the CO2RR. Therefore, the active/stable phase for CO2RR is metallic copper, independent of its initial phase, with a significant change in its morphology upon its reduction yielding the formation of a rougher surface with a higher number of underco-ordinated sites. Thus, the initial thermal oxidation of copper in air controls the reaction activity/selectivity because of the changes induced in the electrode surface morphology/roughness and the presence of more undercoordinated sites during the CO2RR

The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO‐CeO₂ Catalysts

Electronic metal–support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO‐CeO2 redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X‐ray absorption spectroscopy, synchrotron X‐ray powder diffraction, near ambient pressure near edge X‐ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal–support–carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO2, carbonate, or carbonyl species in C1 chemistry

Quantification of inaccurate diagnosis of COPD in primary care medicine: An analysis of the COACH clinical audit

Background: Inaccurate diagnosis in COPD is a current problem with relevant consequences in terms of inefficient health care, which has not been thoroughly studied in primary care medicine. The aim of the present study was to evaluate the degree of inaccurate diagnosis in Primary Care in Spain and study the determinants associated with it. Methods: The Community Assessment of COPD Health Care (COACH) study is a national, observational, randomized, non-interventional, national clinical audit aimed at evaluating clinical practice for patients with COPD in primary care medicine in Spain. For the present analysis, a correct diagnosis was evaluated based on previous exposure and airway obstruction with and without the presence of symptoms. The association of patient-level and center-level variables with inaccurate diagnosis was studied using multivariate multilevel binomial logistic regression models. Results: During the study 4,307 cases from 63 centers were audited. The rate of inaccurate diagnosis was 82.4% (inter-regional range from 76.8% to 90.2%). Patient-related interventions associated with inaccurate diagnosis were related to active smoking, lung function evaluation, and specific therapeutic interventions. Center-level variables related to the availability of certain complementary tests and different aspects of the resources available were also associated with an inaccurate diagnosis. Conclusions: The prevalence data for the inaccurate diagnosis of COPD in primary care medicine in Spain establishes a point of reference in the clinical management of COPD. The descriptors of the variables associated with this inaccurate diagnosis can be used to identify cases and centers in which inaccurate diagnosis is occurring considerably, thus allowing for improvement

The strong gravitational lens finding challenge

Large-scale imaging surveys will increase the number of galaxy-scale strong lensing candidates by maybe three orders of magnitudes beyond the number known today. Finding these rare objects will require picking them out of at least tens of millions of images, and deriving scientific results from them will require quantifying the efficiency and bias of any search method. To achieve these objectives automated methods must be developed. Because gravitational lenses are rare objects, reducing false positives will be particularly important. We present a description and results of an open gravitational lens finding challenge. Participants were asked to classify 100 000 candidate objects as to whether they were gravitational lenses or not with the goal of developing better automated methods for finding lenses in large data sets. A variety of methods were used including visual inspection, arc and ring finders, support vector machines (SVM) and convolutional neural networks (CNN). We find that many of the methods will be easily fast enough to analyse the anticipated data flow. In test data, several methods are able to identify upwards of half the lenses after applying some thresholds on the lens characteristics such as lensed image brightness, size or contrast with the lens galaxy without making a single false-positive identification. This is significantly better than direct inspection by humans was able to do. Having multi-band, ground based data is found to be better for this purpose than single-band space based data with lower noise and higher resolution, suggesting that multi-colour data is crucial. Multi-band space based data will be superior to ground based data. The most difficult challenge for a lens finder is differentiating between rare, irregular and ring-like face-on galaxies and true gravitational lenses. The degree to which the efficiency and biases of lens finders can be quantified largely depends on the realism of the simulated data on which the finders are trained

Electron quantum metamaterials in van der Waals heterostructures

In recent decades, scientists have developed the means to engineer synthetic periodic arrays with feature sizes below the wavelength of light. When such features are appropriately structured, electromagnetic radiation can be manipulated in unusual ways, resulting in optical metamaterials whose function is directly controlled through nanoscale structure. Nature, too, has adopted such techniques -- for example in the unique coloring of butterfly wings -- to manipulate photons as they propagate through nanoscale periodic assemblies. In this Perspective, we highlight the intriguing potential of designer sub-electron wavelength (as well as wavelength-scale) structuring of electronic matter, which affords a new range of synthetic quantum metamaterials with unconventional responses. Driven by experimental developments in stacking atomically layered heterostructures -- e.g., mechanical pick-up/transfer assembly -- atomic scale registrations and structures can be readily tuned over distances smaller than characteristic electronic length-scales (such as electron wavelength, screening length, and electron mean free path). Yet electronic metamaterials promise far richer categories of behavior than those found in conventional optical metamaterial technologies. This is because unlike photons that scarcely interact with each other, electrons in subwavelength structured metamaterials are charged, and strongly interact. As a result, an enormous variety of emergent phenomena can be expected, and radically new classes of interacting quantum metamaterials designed

Defending the genome from the enemy within:mechanisms of retrotransposon suppression in the mouse germline

The viability of any species requires that the genome is kept stable as it is transmitted from generation to generation by the germ cells. One of the challenges to transgenerational genome stability is the potential mutagenic activity of transposable genetic elements, particularly retrotransposons. There are many different types of retrotransposon in mammalian genomes, and these target different points in germline development to amplify and integrate into new genomic locations. Germ cells, and their pluripotent developmental precursors, have evolved a variety of genome defence mechanisms that suppress retrotransposon activity and maintain genome stability across the generations. Here, we review recent advances in understanding how retrotransposon activity is suppressed in the mammalian germline, how genes involved in germline genome defence mechanisms are regulated, and the consequences of mutating these genome defence genes for the developing germline

Evaporation kinetics in swollen porous polymeric networks

Ponencia presentada en el Congreso Euromar 2014.Fil: Velasco, Manuel Isaac. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Silletta, Emilia Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Monti, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Acosta, Rodolfo Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Velasco, Manuel Isaac. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Silletta, Emilia Victoria. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Monti, Gustavo Alberto. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Acosta, Rodolfo Héctor. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Gomez, Cesar Gerardo. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina.Fil: Strumia, Miriam Cristina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina.Fil: Gomez, Cesar Gerardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto Multidisciplinario de Biología Vegetal; Argentina.Fil: Gomez, Cesar Gerardo. Universidad Nacional de Córdoba. Instituto Multidisciplinario de Biología Vegetal; Argentina.Fil: Strumia, Miriam Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto Multidisciplinario de Biología Vegetal; Argentina.Fil: Strumia, Miriam Cristina. Universidad Nacional de Córdoba. Instituto Multidisciplinario de Biología Vegetal; Argentina.Polymer matrices with well defined structure and pore sizes are widely used in several areas of chemistry such as catalysis, enzyme immobilization, HPLC, adsorbents or controlled drug release. These polymers have pores in its structure both in the dry and swollen state. Although it is well known that the structures and properties greatly differ between these two states, only few methods provide information about the swollen one, even though most of the applications involve the matrices in this situation. Nuclear Magnetic Resonance (NMR) is a suitable tool for the study of the molecular dynamics of different liquids spatially confined in macro, meso and nanopores, through changes in the relaxation times. In transverse relaxation experiments, either diffusion inside the pore, or relaxation induced by mobility restriction of the liquid near the wall, are additional sources of relaxation, which are extremely useful in the determination of structural and functional properties.Fil: Velasco, Manuel Isaac. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Silletta, Emilia Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Monti, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Acosta, Rodolfo Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Física Enrique Gaviola; Argentina.Fil: Velasco, Manuel Isaac. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Silletta, Emilia Victoria. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Monti, Gustavo Alberto. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Acosta, Rodolfo Héctor. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina.Fil: Gomez, Cesar Gerardo. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina.Fil: Strumia, Miriam Cristina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina.Fil: Gomez, Cesar Gerardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto Multidisciplinario de Biología Vegetal; Argentina.Fil: Gomez, Cesar Gerardo. Universidad Nacional de Córdoba. Instituto Multidisciplinario de Biología Vegetal; Argentina.Fil: Strumia, Miriam Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto Multidisciplinario de Biología Vegetal; Argentina.Fil: Strumia, Miriam Cristina. Universidad Nacional de Córdoba. Instituto Multidisciplinario de Biología Vegetal; Argentina.Física de los Materiales Condensado