NUEVOS MATERIALES CARBONOSOS COMO CATALIZADORES HETEROGÉNEOS Y SU APLICACIÓN EN PROCESOS DE OXIDACIÓN AVANZADA Y EN REACCIONES DE INTERÉS INDUSTRIAL

En los últimos años, el aumento de la contaminación tanto de la atmósfera como de los suelos y recursos hídricos del planeta ha alcanzado niveles en grado no aceptable por el medio ambiente. En el caso de la contaminación de aguas, ya sea por uso doméstico en aglomeraciones urbanas o por vertidos industriales, estos niveles han llevado a la necesidad de la exigencia del tratamiento de las aguas por necesidad y por ley. Por ello, es importante el desarrollo y optimización de nuevos procesos aplicables a la descontaminación de aguas. En este contexto, en la presente tesis doctoral se describe el desarrollo de nuevos catalizadores basados en carbono altamente eficientes en tratamientos de descontaminación de aguas residuales industriales. Estos materiales basados en carbono garantizan una mayor sostenibilidad de cara a los procesos convencionales de tratamientos de aguas. Así, en una primera parte de la tesis se describe el empleo de materiales carbonosos como soporte de nanopartículas metálicas, obteniendo catalizadores altamente eficientes y con una elevada actividad catalítica en la reacción de foto-Fenton para el tratamiento de aguas residuales industriales. En la segunda parte de la tesis se describe el empleo de materiales grafénicos como catalizadores libres de metales para las reacciones de Fenton y foto-Fenton, reacciones que hasta los últimos años se creía que sólo se podían llevar a cabo con catalizadores metálicos.En els últims anys, l'augment de la contaminació tant de l'atmosfera com dels sòls i recursos hídrics del planeta ha aconseguit nivells en grau no acceptable pel medi ambient. En el cas de la contaminació d'aigües, ja siga per ús domèstic en aglomeracions urbanes o per abocaments industrials, aquests nivells han portat a la necessitat de l'exigència del tractament de les aigües per necessitat i per llei. Per això, és important el desenvolupament i optimització de nous processos aplicables a la descontaminació d'aigües. En aquest context, en la present tesi doctoral es descriu el desenvolupament de nous catalitzadors basats en carboni altament eficients en tractaments de descontaminació d'aigües residuals industrials. Aquests materials basats en carboni garanteixen una major sostenibilitat de cara als processos convencionals de tractaments d'aigües. Així, en una primera part de la tesi es descriu l'ocupació de materials basats en carboni com a suport de nanopartícules metàl·liques, obtenint catalitzadors altament eficients i amb una elevada activitat catalítica en la reacció de foto-Fenton per al tractament d'aigües residuals industrials. En la segona part de la tesi es descriu l'ocupació de materials grafènics com a catalitzadors lliures de metalls per a les reaccions de Fenton i foto-Fenton, reaccions que fins als últims anys es creia que només es podien dur a terme amb catalitzadors metàl·lics.In the last years, the increase in pollution of both the atmosphere and the soil and water resources of the planet has reached levels that are not acceptable to the environment. In the case of water pollution, either by domestic use in urban agglomerations or by industrial discharges, these levels have led to the need for the requirement of water treatment by necessity and by law. Therefore, it is important to develop and optimize new processes applicable to water decontamination. In this context, the present doctoral thesis describes the development of new highly efficient carbon-based catalysts in industrial wastewater decontamination treatments. These carbon-based materials ensure greater sustainability for the conventional water treatment processes. Thus, in a first part of the thesis it is described the use of carbonaceous materials as support for metal nanoparticles, obtaining highly efficient catalysts with a high catalytic activity in the photo-Fenton reaction for industrial wastewater treatments. The second part of the thesis describes the use of graphene materials as metal-free catalysts for the Fenton and photo-Fenton reactions, reactions that until recent years it was believed that could only be carried out with metal catalysts.Espinosa López, JC. (2018). NUEVOS MATERIALES CARBONOSOS COMO CATALIZADORES HETEROGÉNEOS Y SU APLICACIÓN EN PROCESOS DE OXIDACIÓN AVANZADA Y EN REACCIONES DE INTERÉS INDUSTRIAL [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/113414TESI

EL VALOR DE LAS RECOMENDACIONES DE CONSENSO DE LOS ANALISTAS FINANCIEROS EN EL MERCADO DE CAPITALES ESPAÑOL

In this paper we examine the value of analysts’ stock recommendations in the Spanish capital market in the period 1994-2003, using data from JCF Quant. In every month of the sample period the assets have been classified into five portfolios first attending its consensus recommendations level and second by changes of consensus level. The portfolio recommendations returns have been estimated using different models in the context of the portfolio calendar-time methodology. The results obtained show that sell-side analysts are able to detect profitable investment opportunities. Investors could obtain significant positive risk adjusted abnormal returns buying the best recommended assets and selling simultaneously the worst consensus stocks. However a portion of these returns could be attributed to their tendency to recommend the acquisition of big “value” stocks and the sell of small shares with negative prices momentum. Finally, the value of analyst’s recommendations is independent of the firm information level approached by the company size and the number of analysts following it. En este trabajo se analiza el valor de las recomendaciones de inversión de los analistas financieros en el mercado de capitales español en el periodo 1994-2003, con datos procedentes de JCF Quant. Los activos se han clasificado cada mes del periodo muestral en cinco carteras en función del nivel de consenso de las recomendaciones y de sus variaciones. La rentabilidad de las carteras de recomendaciones (cambios) se ha estimado utilizando modelizaciones alternativas con una metodología de tiempo de calendario. Los resultados obtenidos muestran que los analistas identifican oportunidades de inversión rentables, dado que con una estrategia de inversión autofinanciada, consistente en comprar la cartera con recomendaciones más favorables y vender la cesta de activos con peores recomendaciones, se pueden obtener rentabilidades significativamente positivas incluso después de ajustar por riesgo. Parte de esta rentabilidad no es atribuible a su propia capacidad sino a la tendencia a recomendar la compra de activos grandes de valor y la venta de activos pequeños con momentum de precios negativo. Finalmente, el valor de las recomendaciones no parece depender del nivel de información existente sobre las empresas aproximado por el tamaño de las empresas o el número de analistas.Analistas del lado de la venta; Valor de las recomendaciones, Evaluación resultados de carteras Sell-side research; Value of analysts’ recommendations, Performance evaluation, calendar time-portfolios

Approaching long genomic regions and large recombination rates with msParSm as an alternative to MaCS

The msParSm application is an evolution of msPar, the parallel version of the coalescent simulation program ms, which removes the limitation for simulating long stretches of DNA sequences with large recombination rates, without compromising the accuracy of the standard coalescence. This work introduces msParSm, describes its significant performance improvements over msPar and its shared memory parallelization details, and shows how it can get better, if not similar, execution times than MaCS. Two case studies with different mutation rates were analyzed, one approximating the human average and the other approximating the Drosophila melanogaster average. Source code is available at https://github.com/cmontemuino/msparsm

Engineering Active Sites in Reduced Graphene Oxide: Tuning the Catalytic Activity for Aerobic Oxidation

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.9b02237."[EN] The influence of the graphene oxide (GO) reduction method on the activity of the resulting reduced graphene oxide (rGO) for the aerobic oxidation of benzylamine is reported. Starting from GO obtained by the Hummers method, a series of rGO samples were obtained either by chemical (hydroquinone (HQ), hydrazine (HZ) or ascorbic acid (ASC)) or by thermal reduction were prepared. Analytical and spectroscopic techniques provide evidence showing that chemical reducing agents reduce GO with different functional groups that influence the catalytic activity of the resulting rGO for the activation of molecular oxygen in benzylamine oxidation. The highest activity in the aerobic oxidation of benzylamine at 80 degrees C was found for the rGO-HQ1 sample prepared using HQ as a reducing agent. It is proposed that HQ introduces hydroquinone/p-benzoquinone-like moieties on the graphene sheet that act as active sites in the oxidation reaction. This proposal is supported by the activity of HQand/or p-benzoquinone as organocatalysts and by selective masking of oxygen-functional groups present in the most active rGO sample. The most active rGO sample exhibited good reusability and stability in five consecutive uses. Selective quenching experiments revealed that hydroperoxyl radicals are the primary reactive oxygen species generated in the system.Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. S.N. thanks financial support by the Fundacion RamOn Areces (XVIII Concurso Nacional para la Adjudication de Ayudas a la Investigation en Ciencias de la Vida y de la Materia, 2016) and Ministerio de Ciencia, Innovation y Universidades RTI2018-099482-A-I00 project and Generalitat Valenciana (grupos de investigation consolidables 2019, AICO/2019/214). A.D. thanks the University Grants Commission, New Delhi, for the award of an Assistant Professorship under its Faculty Recharge Programme. A.D. also thanks the Department of Science and Technology, India, for the financial support through Extramural Research Funding (EMR/2016/006500).Espinosa-López, JC.; Alvaro Rodríguez, MM.; Dhakshinamoorthy, A.; Navalón Oltra, S.; García Gómez, H. (2019). Engineering Active Sites in Reduced Graphene Oxide: Tuning the Catalytic Activity for Aerobic Oxidation. ACS Sustainable Chemistry & Engineering. 7(19):15948-15956. https://doi.org/10.1021/acssuschemeng.9b02237S159481595671

Fortalecimiento de la cultura de reporte y gestión de sucesos de seguridad del paciente en la UCI para adultos del Hospital Federico Lleras Acosta E.S.E.

“Se calcula que uno de cada diez pacientes sufre algún tipo de daño durante la permanencia en el hospital, el 50% de esos efectos adversos se pudieron prevenir o minimizar el daño. La probabilidad de que un pasajero sufra un daño en un avión es de 1 por cada millón de pasajeros”. (Organizacion Mundial de la Salud, s.f.). La práctica médica es una actividad que se ejerce con muchos riesgos a pesar de todos los avances tecnológicos y protocolos de atención que existen en los hospitales. En muchas ocasiones la atención en salud genera un daño no intencional que se conoce como evento adverso. Con el presente estudio se pretende realizar un enfoque en el tema del fortalecimiento de la cultura del reporte de los sucesos de seguridad en la Unidad de Cuidados Intensivos para Adultos en el Hospital Federico Lleras Acosta de la ciudad de Ibagué. Al analizar la información de los registros donde se reportaron los eventos adversos en la Unidad de Cuidados Intensivos, se evidenció no seguimiento ni gestión adecuada de los sucesos de seguridad que se presentaron durante el año 2018. Es así como se buscará plantear un plan de mejora que permita fortalecer la cultura del reporte y la gestión de sucesos de seguridad en la Unidad de Cuidados Intensivos de Adultos de E.S.E Hospital Federico Lleras Acosta. Para alcanzar esto, se ejecuta un análisis de la institución en 3 capítulos que son: Gerencia Estratégica y de Servicios, Auditoría y Control de Calidad en Salud y Desarrollo Organizacional.EspecializaciónEspecialista En Gerencia De La Salu

Studying the Properties of PVdF-HFP Based Lithium Polymer Electrolytes Using non-ionic Surfactants as Plasticizers

[EN] In this study, two different non-ionic surfactants have been evaluated as a plasticizer in lithium polymer electrolytes and compared with an organic carbonate-based plasticizer. To that end, non-ionic surfactants with different molecular weight and structure have been selected (Triton? X-100 and Brij?L23) and compared with organic carbonates (EC:DEC1:1) as plasticizers in lithium polymer electrolytes. The effect of the plasticizer content, salt content and surfactant characteristics on properties such as ionic conductivity, thermal stability and electrochemical stability of lithium polymer electrolytes has been studied. The results obtained show that the non-ionic surfactants studied as plasticizers (Triton? X-100 and Brij?L23) give lithium polymer electrolytes with higher thermal and electrochemical stability than organic carbonates, thus making them promising plasticizers for lithium polymer electrolytes, especially for high voltage lithium-ion batteries. Surfactant structure could influence the ionic conductivity of the polymer electrolytes, with the linear surfactants being more suitable for this application.This research was funded by the Centro de Desarrollo Tecnologico Industrial-CDTI (ALMAGRID Project-CER-20191006) and by the Instituto Valenciano de Competitividad EmpresarialIVACE-FEDER (MATER Project-IMDEEA/2019/48)Zubizarreta Saenz De Zaitegui, L.; Gil Agustí, MT.; Espinosa-López, JC.; García Pellicer, M.; Quijano-Lopez, A. (2021). Studying the Properties of PVdF-HFP Based Lithium Polymer Electrolytes Using non-ionic Surfactants as Plasticizers. Materiale Plastice. 58(1):237-247. https://doi.org/10.37358/mp.21.1.5463S23724758

Catalytic Ozonation Using Edge-Hydroxylated Graphite-Based Materials

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.9b04646"[EN] This work reports the catalytic ozonation activity of high surface area graphite materials selectively functionalized at the edges with hydroxyl groups. The graphite-based catalyst shows higher activity than the parent graphite, commercial activated carbon, commercial multiwall carbon nanotubes, commercial diamond nanoparticles, graphene oxide, or reduced graphene oxide. Importantly, the catalytic activity of the graphite-based material is also higher than those of benchmark ozonation catalysts such as Co3O4 or Fe2O3. The graphite catalyst was reused up to 10 times with only a minor decrease in the catalytic activity. Catalytic activation of O-3 leads to the generation of hydroperoxide radicals and O-1(2). These results have been interpreted as derived from the combination of a suitable work function and the presence of phenolic/semiquinone-like redox pairs, as well as high dispersibility in water due to the presence of -OH groups. This work highlights the possibility of engineering active and stable carbocatalysts for reactions typically promoted by transition metals.Financial support by the Spanish Ministry of Science and Innovation (Severn Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. S.N. is thankful for financial support from the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudication de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovacion y Universidades RTI2018-099482-A-I00 project and Generalitat Valenciana grupos de investigacion consolidables 2019 (ref: AICO/2019/214) project.Bernat-Quesada, F.; Espinosa-López, JC.; Barbera, V.; Alvaro Rodríguez, MM.; Galimberti, M.; Navalón Oltra, S.; García Gómez, H. (2019). Catalytic Ozonation Using Edge-Hydroxylated Graphite-Based Materials. ACS Sustainable Chemistry & Engineering. 7(20):17443-17452. https://doi.org/10.1021/acssuschemeng.9b04646S174431745272

Eficiencia energética de computadores personales: un análisis comparativo

The demand for electricity related to Information and Communication Technologies is constantly growing and contributing significantly to the increase in global greenhouse gas emissions. To reduce this harmful growth, it is necessary to approach the problem from different perspectives. One of them is to implement changes of scale, such as migrating, if possible, algorithms and processes to more energy efficient resources. In this context, this article explores the possibility of running scientific and engineering programs on personal computers and compares the energy efficiency obtained on these devices with that of more powerful computers and even supercomputers. As an anecdote, it shows how the energy efficiency obtained for the same workloads in personal computers is similar to that of some supercomputers included in the Green500 ranking.La demanda de electricidad relacionada con las Tecnologías de la Información y la Comunicación está en constante crecimiento y contribuyendo significativamente al aumento de las emisiones globales de gases de efecto invernadero. Para reducir este crecimiento nocivo, es necesario abordar el problema desde diferentes perspectivas. Una de ellas es implementar cambios de escala, como migrar, si es posible, algoritmos y procesos a recursos energéticamente más eficientes. En este contexto, este artículo explora la posibilidad de ejecutar programas científicos y de ingeniería en computadores personales y compara la eficiencia energética obtenida en estos dispositivos con la de computadores más potentes e incluso supercomputadores. Como anécdota, se muestra cómo la eficiencia energética obtenida para las mismas cargas de trabajo en computadores personales es similar a la de algunos supercomputadores incluidos en el ranking Green500.Investigación financiada parcialmente por el Ministerio de Ciencia, Innovación y Universidades (MICIU) junto con el Fondo Europeo de Desarrollo Regional (FEDER), proyecto PGC2018-098813-B-C31

Engineering of activated carbon surface to enhance the catalytic activity of supported cobalt oxide nanoparticles in peroxymonosulfate activation

[EN] Commercial activated carbon has been functionalized by chemical or thermal treatments to introduce surface oxygen functional groups able to anchor small cobalt nanoparticles with superior catalytic activity for peroxymonosulfate activation. The resulting activated carbon supports where characterized by combustion elemental analysis, Fourier-transformed infrared spectroscopy, Raman spectroscopy, isothermal N-2 adsorption, temperature programmed desorption/mass spectrometry, X-ray diffraction and scanning electron microscopy. Activated carbon functionalization by nitric acid resulted the most appropriated method to provide a higher population of oxygenated functional groups able to anchor small cobalt nanoparticles. The catalytic activity of supported oxidized metal nanoparticles (4.7 +/- 0.05 nm) was higher than analogous non-oxidized cobalt nanoparticles (2.9 +/- 0.14 nm). The use of analogous supported oxidized iron or copper nanoparticles resulted in lower catalytic activity. Importantly, the supported oxidized cobalt nanoparticles at 0.2 wt% loading exhibit higher activity than benchmark catalysts such as unsupported Co3O4 solid or even homogeneous Co2+ ions. This is a reflection of the relatively low estimated activation energy for both processes, peroxymonosulfate decomposition and phenol degradation. The estimated activation energy values are about 30 and 32 kJ mol(-1). The stability of the most active catalyst was assessed by performing eight consecutive uses without observing decrease of catalytic activity, neither metal leaching or metal nanoparticle aggregation. Turnover numbers/turnover frequencies values as high as 440(5)/8.10(5)h(-1) for peroxymonosulfate activation and 39.10(3)/68.10(3) h(-1) for phenol degradation at pH 7 and 20 degrees C have been estimated, respectively. Electron paramagnetic resonance measurements and selective quenching experiments revealed that the generated sulfate radicals from peroxymonosulfate rapidly are transformed in highly reactive hydroxyl radicals. In excellent agreement with previous reports, this work demonstrates the importance of an adequate activated carbon functionalization to obtain superior and stable catalysts for peroxymonosulfate activation.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, CTQ2015-65963-CQ-R1) and CTQ2014-53292-R is gratefully acknowledged. Generalitat Valenciana is also thanked for funding (Prometeo 2017/083). S.N. thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016).Espinosa-López, JC.; Manickam-Periyaraman, P.; Bernat-Quesada, F.; Sivanesan, S.; Alvaro Rodríguez, MM.; García Gómez, H.; Navalón Oltra, S. (2019). Engineering of activated carbon surface to enhance the catalytic activity of supported cobalt oxide nanoparticles in peroxymonosulfate activation. Applied Catalysis B Environmental. 249:42-53. https://doi.org/10.1016/j.apcatb.2019.02.043S425324

Reduced Graphene Oxide as a Metal-Free Catalyst for the Light-Assisted Fenton-Like Reaction

Natural Sunlight irradiation increases the catalytic activity of reduced graphene oxide (rGO) as metal-free Fenton-like catalyst for phenol degradation. Intermediacy of hydroxyl radicals was proved by electron paramagnetic resonance spectroscopy using a spin trapping agent.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ-2014-53292-R and CTQ-2015-69153-CO2-1) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2013/014).Espinosa López, JC.; Navalón Oltra, S.; Alvaro Rodríguez, MM.; García Gómez, H. (2016). Reduced Graphene Oxide as a Metal-Free Catalyst for the Light-Assisted Fenton-Like Reaction. ChemCatChem. 8(16):2642-2648. https://doi.org/10.1002/cctc.201600364S2642264881