Dinamica estocastica clásica y cuántica de la difusión activada de adsorbatos interactuantes en superficies

Tesis doctoral inédita. Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Física Teórica de la Materia Condensada. Fecha de lectura: 19-06-0

First Principles Calculations on the Stoichiometric and Defective (101) Anatase Surface and Upon Hydrogen and H2Pc Adsorption: The Influence of Electronic Exchange and Correlation and of Basis Set Approximations

Anatase TiO2 provides photoactivity with high chemical stability at a reasonable cost. Different methods have been used to enhance its photocatalytic activity by creating band gap states through the introduction of oxygen vacancies, hydrogen impurities, or the adorption of phthalocyanines, which are usually employed as organic dyes in dye-sensitized solar cells. Predicting how these interactions affect the electronic structure of anatase requires an efficient and robust theory. In order to document the efficiency and accuracy of commonly used approaches we have considered two widely used implementations of density functional theory (DFT), namely the all-electron linear combination of atomic orbitals (AE–LCAO) and the pseudo-potential plane waves (PP–PW) approaches, to calculate the properties of the stoichiometric and defective anatase TiO2 (101) surface. Hybrid functionals, and in particular HSE, lead to a computed band gap in agreement with that measured by using UV adsorption spectroscopy. When using PBE+U, the gap is underestimated by 20 % but the computed position of defect induced gap states relative to the conduction band minimum (CBM) are found to be in good agreement with those calculated using hybrid functionals. These results allow us to conclude that hybrid functionals based on the use of AE–LCAO provide an efficient and robust approach for predicting trends in the band gap and the position of gap states in large model systems. We extend this analysis to surface adsorption and use the AE–LCAO approach with the hybrid functional HSED3 to study the adsorption of the phthalocyanine H2Pc on anatase (101). Our results suggest that H2Pc prefers to be adsorbed on the surface Ti5c rows of anatase (101), in agreement with that seen in recent STM experiments on rutile (110)

Ethanol gas sensing mechanisms of p-type NiO at room temperature

Conductometric gas sensors based on metal oxide semiconductors (MOS) usually require high temperature operation, increasing their energy consumption and limiting their applicability. However, room temperature operation with these devices still remains a challenge in many sensor-analyte systems due in part to the low or null response and recovery speeds obtained at this temperature. In this work, the conductometric response of p-type NiO ceramic samples to ethanol is studied under room temperature operation. An anomalous response consisting in an unexpected resistance decrease upon ethanol exposure is observed depending on sample texturing, which is tuned by changing the temperature at which the samples are synthesized. This anomalous response is characterized by fast response and recovery times. A model based on two competing mechanisms, consisting in either an electron transfer from NiO to the ethanol molecule or the catalytic decomposition of adsorbed ethanol, is proposed to explain the observed anomalous response. Extending this model to other MOS could pave the way for fast sensors operating at room temperatur

Understanding the UV luminescence of zinc germanate: The role of native defects

Achieving efficient and stable ultraviolet emission is a challenging goal in optoelectronic devices. Herein, we investigate the UV luminescence of zinc germanate Zn2GeO4 microwires by means of photoluminescence measurements as a function of temperature and excitation conditions. The emitted UV light is composed of two bands (a broad one and a narrow one) associated with the native defects structure. In addition, with the aid of density functional theory (DFT) calculations, the energy positions of the electronic levels related to native defects in Zn2GeO4 have been calculated. In particular, our results support that zinc interstitials are the responsible for the narrow UV band, which is, in turn, split into two components with different temperature dependence behaviour. The origin of the two components is explained on the basis of the particular location of Zn_i in the lattice and agrees with DFT calculations. Furthermore, a kinetic luminescence model is proposed to ascertain the temperature evolution of this UV emission. These results pave the way to exploit defect engineering in achieving functional optoelectronic devices to operate in the UV region

Assessing aids for the elaboration of argumentative synthesis in the University: Guide or Rubric?

Although most of the interventions to foster the integration of multiple pieces of information has focused on teaching “how” to integrate (Barzilai et al., 2018) providing different kinds of instruction on the processes implied, instruction focusing on the criteria to evaluate integration are scarce and mainly centered on integrating complementary, but not contradictory, sources. In this work we designed and contrasted the effectiveness of two aids to improve the quality of the syntheses written by undergraduates from texts that defended opposing views on a topic: a Guide to the process of preparing a synthesis vs a Rubric with the evaluation criteria of written products. The number of arguments and the degree of integration were examined. Also, the students' perception was assessed regarding the usefulness of the aids to plan, to write and to review their synthesis. Seen that we found that offering a guide accompanied by explicit instruction is more effective than providing it without explicit instruction Mateos et al. (2018), the two aids were offered here under two conditions: Explicit Instruction vs. Traditional Instruction. Thus, we carried out an experimental study with 122 Psychology students, distributed randomly into four intervention programs. In the first and fourth session they performed a synthesis task without support. In the second session, after receiving the instruction (explicit vs. traditional), each student made a new synthesis using the specific aid provided (practice 1, with Guide/Rubric). In the third session the participants carried out another synthesis under analogous conditions (practice 2, with aids). Our results pointed out that, regardless the instruction, both aids (Guide and Rubric) improved the degree of integration of the students’ syntheses. However, the guide contributed better to improve the selection of arguments. Students who received Explicit Instruction found both aids to be equally useful for planning and writing their syntheses. In contrast, after Traditional Instruction the Guide was perceived as more useful for planning and writing syntheses. The Guide was more useful for reviewing their texts. We will discuss the implications of these findings for synthesis writing training and conclude with recommendations and suggestions for future studies.2021-2

Influence of cation substitution on the complex structure and luminescent properties of the Zn_kIn_2O_(k+3) system

The effect of In^(3+) substitution by Ga^(3+) or Al^(3+) on the structure and luminescent properties of Zn_7In_(2-x)M_xO_10 (M = Ga or Al; 0 <= x <= 1) oxides has been investigated by means of high spatial resolution X-ray spectroscopy and high-angle annular dark-field images, combined with magic angle spinning nuclear magnetic resonance spectroscopy. Local structural variations have been identified for the Al- and Ga-doped samples through the analysis of atomically resolved chemical maps and the identification of their structural environment within the wurtzite lattice. In3+ is distributed in a zig-zag modulation, while Al^(3+) and Ga^(3+) are located in a flat distribution at the center of the wurtzite block. Density functional theory calculations provide unambiguous evidence for the preferential flat location of Ga^(3+) and Al^(3+) associated with the different strains introduced in the structure as a result of their ionic radii. The characterization of the photoluminescence response reveals the appearance of new radiative recombination pathways for the doped materials because of the presence of new defect levels in the band gap of the Zn_7In_2O_10 structure

patrimonio intelectual

Actas de congresoLas VI Jornadas se realizaron con la exposición de ponencias que se incluyeron en cuatro ejes temáticos, que se desarrollaron de modo sucesivo para facilitar la asistencia, el intercambio y el debate, distribuidos en tres jornadas. Los ejes temáticos abordados fueron: 1. La enseñanza como proyecto de investigación. Recursos de enseñanza-aprendizaje como mejoras de la calidad educativa. 2. La experimentación como proyecto de investigación. Del ensayo a la aplicabilidad territorial, urbana, arquitectónica y de diseño industrial. 3. Tiempo y espacio como proyecto de investigación. Sentido, destino y usos del patrimonio construido y simbólico. 4. Idea constructiva, formulación y ejecución como proyecto de investigación. Búsqueda y elaboración de resultados que conforman los proyectos de la arquitectura y el diseño

Mortality from gastrointestinal congenital anomalies at 264 hospitals in 74 low-income, middle-income, and high-income countries: a multicentre, international, prospective cohort study

Summary Background Congenital anomalies are the fifth leading cause of mortality in children younger than 5 years globally. Many gastrointestinal congenital anomalies are fatal without timely access to neonatal surgical care, but few studies have been done on these conditions in low-income and middle-income countries (LMICs). We compared outcomes of the seven most common gastrointestinal congenital anomalies in low-income, middle-income, and high-income countries globally, and identified factors associated with mortality. Methods We did a multicentre, international prospective cohort study of patients younger than 16 years, presenting to hospital for the first time with oesophageal atresia, congenital diaphragmatic hernia, intestinal atresia, gastroschisis, exomphalos, anorectal malformation, and Hirschsprung’s disease. Recruitment was of consecutive patients for a minimum of 1 month between October, 2018, and April, 2019. We collected data on patient demographics, clinical status, interventions, and outcomes using the REDCap platform. Patients were followed up for 30 days after primary intervention, or 30 days after admission if they did not receive an intervention. The primary outcome was all-cause, in-hospital mortality for all conditions combined and each condition individually, stratified by country income status. We did a complete case analysis. Findings We included 3849 patients with 3975 study conditions (560 with oesophageal atresia, 448 with congenital diaphragmatic hernia, 681 with intestinal atresia, 453 with gastroschisis, 325 with exomphalos, 991 with anorectal malformation, and 517 with Hirschsprung’s disease) from 264 hospitals (89 in high-income countries, 166 in middleincome countries, and nine in low-income countries) in 74 countries. Of the 3849 patients, 2231 (58·0%) were male. Median gestational age at birth was 38 weeks (IQR 36–39) and median bodyweight at presentation was 2·8 kg (2·3–3·3). Mortality among all patients was 37 (39·8%) of 93 in low-income countries, 583 (20·4%) of 2860 in middle-income countries, and 50 (5·6%) of 896 in high-income countries (p<0·0001 between all country income groups). Gastroschisis had the greatest difference in mortality between country income strata (nine [90·0%] of ten in lowincome countries, 97 [31·9%] of 304 in middle-income countries, and two [1·4%] of 139 in high-income countries; p≤0·0001 between all country income groups). Factors significantly associated with higher mortality for all patients combined included country income status (low-income vs high-income countries, risk ratio 2·78 [95% CI 1·88–4·11], p<0·0001; middle-income vs high-income countries, 2·11 [1·59–2·79], p<0·0001), sepsis at presentation (1·20 [1·04–1·40], p=0·016), higher American Society of Anesthesiologists (ASA) score at primary intervention (ASA 4–5 vs ASA 1–2, 1·82 [1·40–2·35], p<0·0001; ASA 3 vs ASA 1–2, 1·58, [1·30–1·92], p<0·0001]), surgical safety checklist not used (1·39 [1·02–1·90], p=0·035), and ventilation or parenteral nutrition unavailable when needed (ventilation 1·96, [1·41–2·71], p=0·0001; parenteral nutrition 1·35, [1·05–1·74], p=0·018). Administration of parenteral nutrition (0·61, [0·47–0·79], p=0·0002) and use of a peripherally inserted central catheter (0·65 [0·50–0·86], p=0·0024) or percutaneous central line (0·69 [0·48–1·00], p=0·049) were associated with lower mortality. Interpretation Unacceptable differences in mortality exist for gastrointestinal congenital anomalies between lowincome, middle-income, and high-income countries. Improving access to quality neonatal surgical care in LMICs will be vital to achieve Sustainable Development Goal 3.2 of ending preventable deaths in neonates and children younger than 5 years by 2030

First principles calculations on the stoichiometric and defective (101) anatase surface and upon hydrogen and H2Pc adsorption

Anatase TiO2 provides photoactivity with high chemical stability at a reasonable cost. Different methods have been used to enhance its photocatalytic activity by creating band gap states through the introduction of oxygen vacancies, hydrogen impurities, or the adorption of phthalocyanines, which are usually employed as organic dyes in dye-sensitized solar cells. Predicting how these interactions affect the electronic structure of anatase requires an efficient and robust theory. In order to document the efficiency and accuracy of commonly used approaches we have considered two widely used implementations of density functional theory (DFT), namely the all-electron linear combination of atomic orbitals (AE-LCAO) and the pseudo-potential plane waves (PP-PW) approaches, to calculate the properties of the stoichiometric and defective anatase TiO2 (101) surface. Hybrid functionals, and in particular HSE,lead to a computed band gap in agreement with that measured by using UV adsorption spectroscopy. When using PBE+U, the gap is underestimated by 20 % but the computed position of defect induced gap states relative to the conduction band minimum (CBM) are found to be in good agreement with those calculated using hybrid functionals. These results allow us to conclude that hybrid functionals based on the use of AE-LCAO provide an efficient and robust approach for predicting trends in the band gap and the position of gap states in large model systems. We extend this analysis to surface adsorption and use the AE-LCAO approach with the hybrid functional HSED3 to study the adsorption of the phthalocyanine H 2 Pc on anatase (101). Our results suggest that H 2 Pc prefers to be adsorbed on the surface Ti 5c rows of anatase (101), in agreement with that seen in recent STM experiments on rutile (110).Peer reviewe

Ethanol gas sensing mechanisms of p-type NiO at room temperature

CRUE-CSIC (Acuerdos Transformativos 2021) © 2021 The Authors. This work was supported by the V-PRICIT of Comunidad de Madrid through the research project PR65/19-22335 and by the RTI2018-097195-B-I00 project supported by MCI/AEI/FEDER, UE. Authors thank the ESCA-microscopy staff at the Elettra Synchrotron for their help during XPS and additional sensitivity measurements. J.B. acknowledges financial support from the Comunidad de Madrid through the Talento fellowship 2017-T2/IND-5617.Conductometric gas sensors based on metal oxide semiconductors (MOS) usually require high temperature operation, increasing their energy consumption and limiting their applicability. However, room temperature operation with these devices still remains a challenge in many sensor-analyte systems due in part to the low or null response and recovery speeds obtained at this temperature. In this work, the conductometric response of ptype NiO ceramic samples to ethanol is studied under room temperature operation. An anomalous response consisting in an unexpected resistance decrease upon ethanol exposure is observed depending on sample texturing, which is tuned by changing the temperature at which the samples are synthesized. This anomalous response is characterized by fast response and recovery times. A model based on two competing mechanisms, consisting in either an electron transfer from NiO to the ethanol molecule or the catalytic decomposition of adsorbed ethanol, is proposed to explain the observed anomalous response. Extending this model to other MOS could pave the way for fast sensors operating at room temperature.Ministerio de Ciencia e Innovación (MICINN)/FEDERComunidad de MadridDepto. de Física de MaterialesFac. de Ciencias FísicasTRUEpu