Análisis de la fractalidad temporal de la precipitación en Cataluña, España (2010)

Se han contabilizado los intervalos con precipitación, a resoluciones de 30 minutos hasta 48 horas, de once observatorios de Cataluña durante el año 2010. Con esto se ha analizado la fractalidad temporal de la precipitación, que tiene su expresión numérica en el concepto de la dimensión fractal (D) y que es representativa de la mayor o menor regularidad temporal de la precipitación. Asimismo, se han comparado para los mismos once observatorios las dimensiones fractales del semestre cálido y del semestre frío, con valores en general mayores en este último. El patrón espacial básico anual y del semestre cálido de D muestran un aumento de los valores desde el suroeste hacia el nordeste

Sequías en Chile central a partir de diferentes índices en el período 1981-2010

The different dimensions of meteorological drought in central Chile in order to characterize their occurrence at multiple time scales and find evidence of variability and change in frequency are analyzed. For that, there are 27 meteorological stations at daily resolution arranged, which allow the identification of dry periods under the threshold of 0.1 mm. Besides establishing dry spells and its persistence (using the Besson index), the standard precipitation index (SPI) was applied to determine the internanual varibilidad of drought, precisely in a region with semiarid and Mediterranean climate. The results show greater persistence of dry days in the region of Valparaíso, which is consistent with the length of dry spells in many cases exceeding 22 days a year. The event La Niña in the winter of 1998 caused the longest streak of dry days of the rainy trimester (67 days), totaling 86 days without rain. However, it has not been able to prove their variability and changes in frequency.Se analizan las diferentes dimensiones de la sequía meteorológica en Chile central con el propósito de caracterizar su ocurrencia a múltiples escalas temporales y encontrar indicios de cambio en su variabilidad y frecuencia. Para ello se ha dispuesto de 27 estaciones meteorológicas a resolución diaria, las cuales permiten identificar períodos secos bajo el umbral 0,1 mm. Además de establecer las rachas de sequías y su persistencia (mediante el índice de Besson), se aplicó el índice estándar de precipitación (SPI) para conocer la varibilidad internanual de la sequía, justamente en una región de clima semiárido y mediterráneo. Los resultados indican mayor persistencia de días secos en la región de Valparaíso, lo cual es consistente con la longitud de las rachas de sequía, en muchos casos superior a 22 días al año. El evento La Niña en el invierno de 1998 provocó la mayor racha de días secos del trimestre lluvioso (67 días), sumando en total 86 días sin lluvia. No obstante, no se ha podido probar cambios en su variabilidad y frecuencia

CLÚSTERES MOLECULARES DE ORO, PALADIO Y COBRE COMO CATALIZADORES DE REACCIONES ORGÁNICAS

En la presente tesis doctoral se ha realizado un estudio sobre las especies catalíticamente activas en reacciones de formación de enlace carbono-carbono y carbono-heteroátomo catalizadas por oro, paladio y cobre. En el caso de las reacciones catalizadas por oro (sales de Au+ o Au3+ complejos de Au+ o nanopartículas de Au), se ha comprobado que, independientemente del catalizador de oro de partida, las especies catalíticamente activas en algunas reacciones son clústeres atómicos de oro de entre 2 y 9 átomos, y que, dentro de este rango, las reacciones son sensibles al número de átomos de oro que forman el clúster. Estos clústeres presentan una actividad catalítica inusualmente alta para este tipo de reacciones, llegando a realizar hasta 10 millones de ciclos catalíticos por hora a temperatura ambiente. Además, se ha estudiado la estabilidad de estos clústeres frente a aniones y ligandos en disolución. En el caso de las reacciones de acoplamiento cruzado catalizadas por paladio bajo condiciones de Jeffery (sin ligandos, amida como disolvente, 130-140 oC), se ha observado la formación y actividad catalítica de clústeres de Pd de entre 3 y 4 átomos para las reacciones de acoplamiento de Heck, Sonogashira, Stille y Suzuki. Estos clústeres se estabilizan en presencia de agua o aminas y presentan una alta actividad catalítica para yoduros y bromuros de arilo. También se ha observado la formación de clústeres de Cu en reacciones de acoplamiento entre yoduros de arilo y diversos nucleófilos (amidas, fenoles, fosfinas, tioles, alquinos) en ausencia de ligandos diamina. Además, se ha podido establecer la naturaleza, mecanismo de formación y cantidad de estos clústeres de Cu formados a partir de una sal de partida. Por último, se ha comparado la actividad catalítica de los clústeres de oro, paladio y cobre para reacciones tipo donde se necesita catálisis Lewis, radicalaria o red-ox, pudiendo relacionar la naturaleza fisicoquímica de los clústeres con su actividad catalítica.Oliver Meseguer, J. (2015). CLÚSTERES MOLECULARES DE ORO, PALADIO Y COBRE COMO CATALIZADORES DE REACCIONES ORGÁNICAS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/48566TESISPremios Extraordinarios de tesis doctorale

Hydrogen migration at restructuring palladium-silver oxide boundaries dramatically enhances reduction rate of silver oxide.

Heterogeneous catalysts are complex materials with multiple interfaces. A critical proposition in exploiting bifunctionality in alloy catalysts is to achieve surface migration across interfaces separating functionally dissimilar regions. Herein, we demonstrate the enhancement of more than 104 in the rate of molecular hydrogen reduction of a silver surface oxide in the presence of palladium oxide compared to pure silver oxide resulting from the transfer of atomic hydrogen from palladium oxide islands onto the surrounding surface formed from oxidation of a palladium-silver alloy. The palladium-silver interface also dynamically restructures during reduction, resulting in silver-palladium intermixing. This study clearly demonstrates the migration of reaction intermediates and catalyst material across surface interfacial boundaries in alloys with a significant effect on surface reactivity, having broad implications for the catalytic function of bimetallic materials

Nanotitania catalyzes the chemoselective hydration and alkoxylation of epoxides

[EN] Glycols and ethoxy- and propoxy-alcohols are fundamental chemicals in industry, with annual productions of millions of tons, still manufactured in many cases with corrosive and unrecoverable catalysts such as KOH, amines and BF3 center dot OEt2. Here we show that commercially available, inexpensive, non-toxic, solid and recyclable nanotitania catalyzes the hydration and alkoxylation of epoxides, with water and primary and secondary alcohols but not with phenols, carboxylic acids and tertiary alcohols. In this way, the chemoselective synthesis of different glycols and 1,4-dioxanones, and the implementation of nanotitania for the production in-flow of glycols and alkoxylated alcohols, has been achieved. Mechanistic studies support the key role of vacancies in the nano-oxide catalyst.A.L.-P. thanks the MICIIN (project code PID2020-115100GB-I00) for financial support. J.O.-M. thanks the Juan de la Cierva Program for the concession of a contract (IJC2018-036514-I). J.B.-S. thanks La Caixa Foundation grant (ID 100010434), code LCF/BQ/DI19/11730029.Oliver-Meseguer, J.; Ballesteros-Soberanas, J.; Tejeda-Serrano, M.; Martínez-Castelló, A.; Leyva Perez, A. (2021). Nanotitania catalyzes the chemoselective hydration and alkoxylation of epoxides. Molecular Catalysis. 515:1-11. https://doi.org/10.1016/j.mcat.2021.111927S11151

Precipitación extrema en la Puna del Desierto de Atacama: ¿Cómo gestionar la incertidumbre actual y futura?

Chile is one of the Latin American countries most affected by Climate Change. There is a high level of uncertainty regarding the variability of precipitation and its projections in many regions of this country. This poses challenges for climate characterization and for defining strategies to reduce its risks. The study area is the Puna of Atacama Desert, Andean highlands located to the eastern side of the extreme arid lands, a region that concentrates the main copper and lithium mining at word scale, and where meteorological observations are scarce, with missing data and unreliable projections. Considering this data limitations, a daily precipitation database of 35 weather stations was constructed in order to evaluate some extreme precipitation indices that allow establishing changes between 1981-2017, in addition to spatial interpolations based on topography. It is concluded that most of the meteorological stations do not present significant trends of change, e.g. Extremely wet days (R99p), Wet days (RR) and Consecutive wet days (CWD). The index with the highest number of stations with a trend is CDD, which shows an increase in consecutive dry days. One of the main contributions of this research was to expand the number of observations and to generate maps of the spatial distribution of the indices of extremes. We are facing open questions regarding living with uncertainty, and meeting the challenges of maintaining records to increase the levels of certainty of climatic changes.Chile es uno de los países de América Latina más afectados por el cambio climático. Existe un elevado nivel de incertidumbre respecto a la variabilidad de las precipitaciones y sus proyecciones en muchas de sus regiones. Ello plantea desafíos para su caracterización climática y para definir estrategias para reducir los riesgos asociados. Se estudia la Puna del Desierto de Atacama, paisaje andino de altura que bordea las tierras áridas por el lado este, y que concentran las principales minas de cobre y litio a escala mundial, y donde existen escasas observaciones meteorológicas, con datos perdidos y proyecciones de poca fiabilidad. Es por ello que se construyó una base diaria de precipitación de 35 estaciones con el fin de evaluar algunos índices extremos que permitan establecer cambios entre 1981-2017, además de interpolaciones espaciales basadas en la topografía. Se concluye que la mayoría de las estaciones meteorológicas no presenta tendencias significativas de cambio, destacando días extremadamente húmedos (R99p), días húmedos (RR) y días húmedos consecutivos (CWD). El índice con mayor cantidad de estaciones con tendencia es CDD, que muestra un incremento de los días consecutivos secos. Uno de los principales aportes de esta investigación fue ampliar el número de observaciones y generar mapas de la distribución espacial de los índices de extremos. Nos quedan preguntas abiertas respecto a convivir con la incertidumbre, y alcanzar desafíos de mantener los registros para aumentar los niveles de certeza de los cambios climáticos.The authors acknowledge support by the Program CLIMAT AmSud Project PRELASA (21-CLIMAT-12)

A component-based approximation for trend detection of intense rainfall in the Spanish Mediterranean coast

Rainfall behavior is a fundamental issue in areas with scarce and irregular amounts, such as the Spanish Mediterranean region. We identified 12 spatial patterns that characterized 899 torrential precipitation events (≥150 mm in 24 h) that occurred in the 3,537 rainy precipitation series in the period 1950-2020. Three of these components--eastern and ESE--showed positive and significant trends in their accumulated volumes. We then characterized the mean synoptic causes of the 10 most intense events in each component at both mean sea-level pressure and 500 hPa geopotential height, and also the integrated water-vapor transport between 1,000 and 300 hPa. We found a clear spatial distribution of the pluviometric effects related to unstable atmospheric situations (such as troughs and cut-off lows), and also to SW-SE advection fluxes that brought moist air from the Western Mediterranean. In particular, torrential rainfall in the Balearic Islands related more to E-NE advections than to southeastern ones. We also determined that the major parts of these components occurred in early autumn, especially in September and October. We expect these findings to help our understanding of the processes leading to catastrophic situations along the Spanish Mediterranean coast and to lead to improvements in early alert systems and management plans

Generation and Reactivity of Electron-Rich Carbenes on the Surface of Catalytic Gold Nanoparticles

[EN] The reactive nature of carbenes can be modulated, and ultimately reversed, by receiving additional electron density from a metal. Here, it is shown that Au nanoparticles (NPs) generate an electron-rich carbene on surface after transferring electron density to the carbonyl group of an in situ activated diazoacetate, as assessed by Fourier transformed infrared (FT¿IR) spectroscopy, magic angle spinning nuclear magnetic resonance (MAS NMR), and Raman spectroscopy. Density functional theory (DFT) calculations support the observed experimental values and unveil the participation of at least three different Au atoms during carbene stabilization. The surface stabilized carbene shows an extraordinary stability against nucleophiles and reacts with electrophiles to give new products. These findings showcase the ability of catalytic Au NPs to inject electron density in energetically high but symmetrically allowed valence orbitals of sluggish molecules.Financial support by MINECO through the Severo Ochoa program, RETOS program (CTQ2014-55178-R), and Ramon y Cajal Program (to A.L.-P.) is acknowledged. J.O.-M. thanks ITQ for the concession of a contract. We are thankful for the electron microscopy service of UPV.Oliver-Meseguer, J.; Boronat Zaragoza, M.; Vidal Moya, JA.; Concepción Heydorn, P.; Rivero-Crespo, MÁ.; Leyva Perez, A.; Corma Canós, A. (2018). Generation and Reactivity of Electron-Rich Carbenes on the Surface of Catalytic Gold Nanoparticles. Journal of the American Chemical Society. 140(9):3215-3218. https://doi.org/10.1021/jacs.7b13696S32153218140

Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids

Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal-organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation.This work was supported by the Ministero dell’Istruzione, dell’Università e della Ricerca (Italy) and the MINECO (Spain) (Projects PID2019−104778GB−I00, CTQ 2017–86735–P, RTC–2017–6331–5, Severo Ochoa program SEV–2016–0683 and Excellence Unit “Maria de Maeztu” CEX2019−000919−M). E.T. and M.M. thank MINECO and ITQ for the concession of a contract. D.A. acknowledges the financial support of the Fondazione CARIPLO/“Economia Circolare: ricerca per un futuro sostenibile” 2019, Project code: 2019–2090, MOCA and Diamond Light Source for awarded beamtime and provision of synchrotron radiation facilities and thanks Dr. Sarah Barnett and David Allan for their assistance at I19 beamline (Proposal No. MT18768-1). Thanks are also extended to the “2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011” (J.F.-S.) and “La Caixa” scholarship (ID 100010434) LCF/BQ/DI19/11730029 (J.B.-S). E.P. acknowledges the financial support of the European Research Council under the European Union’s Horizon 2020 research and innovation programme/ERC Grant Agreement No 814804, MOF reactors. J.O.-M. acknowledges the Juan de la Cierva program for the concession of a contract (IJC2018-036514-I). We gratefully acknowledge to ALBA synchrotron for allocating beamtime and CLÆSS beamline staff for their technical support during our experiment. The computations were performed on the Tirant III cluster of the Servei d’Informàtica of the University of Valencia.Peer reviewe