Development of functionalized aerogels for applications as catalyst and hydrides matrix

Los hidruros son una alternativa en el almacenamiento de H2. Estos elementos al ser calentados liberan el combustible. En esta tesis se ha propuesto el confinamiento de hidruros en materiales mesoporosos con el fin de mejoras sus cinéticas de descomposición. Para ello se han desarrollado aerogeles haciendo uso de la tecnología supercrítica. Además se ha modificado la naturaleza química de la superficie de estos soportes, controlando así las interacciones entre el soporte y el material confinado en ellos. Por otro lado, creando aerogeles cuya estructura contiene carbono, se han modificado las propiedades dieléctricas de los mismos. Ésto, ha permitido el uso de microondas para su calentamiento, de una forma más rápida y homogénea, consiguiendo así una liberación de H2 más eficiente y controlada. Por último se ha desarrollado un plan de empresa (LightEnergy) que propone la aplicación de la tecnología desarrollada al mundo de las celdas de combustible.Departamento de Ingeniería Química y Tecnología del Medio AmbienteDoctorado en Ingeniería Química y Ambienta

Enhancement of hydrogen release kinetics from ethane 1,2 diamineborane (EDAB) by micronization using Supercritical Antisolvent (SAS) Precipitation

Ethane 1, 2 diamineborane (EDAB) was micronized from THF solutions using Supercritical Antisolvent (SAS) process. The influence of temperature, solute concentration and carbon dioxide fraction on the final properties of EDAB particles was studied. By SAS micronization, the original prismatic EDAB particles of about 400 µm with a crystallite size of 100 nm were converted into microspheres of less than 2 µm with a crystallite size of 50 nm. This reduction in the particle and grain sizes resulted in an improvement in thermal properties. The kinetics of release of hydrogen by thermolysis at 100ºC was also significantly enhanced due to the reduction in the diffusion length, reducing the time needed for the decomposition of the hydride by a factor of six. Moreover, a suppression of induction time was obtained by destabilization of the hydride after treatment. XRD and FTIR analyses showed that no chemical decomposition and no variation of the crystalline structure took place by SAS processing.2018-07-15Spanish Ministry of Economy and Competitiveness project ENE2014-53459-

Improvement of the kinetics of hydrogen release from ammonia borane confined in silica aerogel

Ammonia borane is a promising hydrogen storage material due to its high gravimetric capacity (19.6 % wt), but it also presents limitations such as a slow hydrogen release with a long induction time, a difficult regeneration, or the formation of foams and gaseous by-products during thermolysis. Previous studies have shown that by nanoconfinement of ammonia borane within a porous support some of these limitations can be overcome due to the reduction and stabilization of ammonia borane particle size. However, this effect was only observed with moderate ammonia borane loadings, as with higher loadings the pores of the support became obstructed. In this work, silica aerogels produced by CO2 drying, with pore volumes up to 2 cm3/g, have been used to confine ammonia borane. The influence of the amount of ammonia borane loaded on the aerogel support on the thermal and structural properties of the material has been analyzed. It has been found that more than 60 wt% of ammonia borane can be effectively stored in the pores of the aerogel support. The resulting material shows faster hydrogen release kinetics by thermolysis at 80ºC, due to a significant reduction in the mea size of ammonia borane after confinement and the participation of SiOH and SiOSi groups of silica aerogel in the decomposition mechanism.2018-09-20Spanish Ministry of Economy and Competitiveness project ENE2011-2454

Tuned Pd/SiO 2 aerogel catalyst prepared by different synthesis techniques

Pd nanoparticles have been embedded on silica aerogel by using three different techniques. In each of them the metal was loaded in the matrix at different steps of the production: the direct synthesis, the wet impregnation and the supercritical impregnation of the previously dried aerogels. The resultant materials have been characterized to analyze the differences depending on the applied technique for its impregnation. Atomic absorption, nitrogen physisorption, X-ray diffraction, infrared spectroscopy and transmission electron microscopy where performed. In all the techniques the concentration of metal has been varied (from 0.13 to 1.61 % wt.) by modifying the concentration of the suspension (Pd-polyvinylpyrrolidone nanoparticles used in the direct synthesis) or of the solution of the metallic precursor (palladium acetylacetonate), both in the organic solvent and the supercritical media. The characterization had generally shown a good distribution of the metallic particles in the matrix, and the negligible effect of the metal on the textural properties. Finally, considerable variations where observed on the silanol groups on the surface of the catalysts. These materials were tested in D-glucose hydrogenation, observing significant differences on the performance of the catalyst depending on the synthesis technique employed.2018-06-06Spanish Ministry of Economy and Competitiveness project ENE2014-53459-

Reversible hydrogen sorption in the composite made of magnesium borohydride and silica aerogel

Magnesium borohydride Mg(BH4)2 is a promising hydrogen storage material as it releases high hydrogen storage capacity at mild desorption temperatures, but it is still limited by slow hydrogen release kinetics and by the harsh conditions required to re-hydrogenate this compound. In this work, composites made of commercial Mg(BH4)2 and synthesized silica aerogel microparticles were prepared by thermal treatment in hydrogen under 120 bar and 200ºC. As a result, the sorption properties of the hydride are improved: calorimetric measurements show that decomposition temperature is reduced by 60ºC, and the typical 3-step decomposition mechanism of Mg(BH4)2 changes to a single-step mechanism in range of 220-400°C. The kinetics of the first dehydrogenation at 300ºC was two times faster in Mg(BH4)2-SiO2 composites than in the case of bulk γ-Mg(BH4)2. Additionally, the re-hydrogenation of this material at comparatively moderate conditions of 390ºC and 110 bar is presented for the first time, achieving cyclability with a reversible release of hydrogen up to 6wt%. Different amounts of hydrogen were exchanged depending on the temperature of desorption (300ºC or 400ºC) and the presence or absence of silica aerogel. This result indicates that silica aerogel chemically interacts with Mg(BH4)2, acting as an additive, which can result in different hydrogenation-dehydrogenation routes in which different amounts and types of intermediates are formed, influencing the kinetics and the cyclability.2018-07-27Spanish Ministry of Economy and Competitiveness project ENE2014-53459-

Release of Hydrogen from Nanoconfined Hydrides by Application of Microwaves

The release of hydrogen from solid hydrides by thermolysis can be improved by nanoconfinement of the hydride in a suitable micro/mesoporous support, but the slow heat transfer by conduction through the support can be a limitation. In this work, a C/SiO2 mesoporous material has been synthesized and employed as matrix for nanoconfinement of hydrides. The matrix showed high surface area and pore volume (386 m²/g and 1.41 cm³/g), which enabled the confinement of high concentrations of hydride. Furthermore, by modification of the proportion between C and SiO2, the dielectric properties of the complex could be modified, making it susceptible to microwave heating. As with this heating method the entire sample is heated simultaneously, the heat transfer resistances associated to conduction were eliminated. To demonstrate this possibility, ethane 1,2-diaminoborane (EDAB) was embedded on the C/SiO2 matrix at concentrations ranging from 11 to 31%wt using a wet impregnation method, and a device appropriate for hydrogen release from this material by application of microwaves was designed with the aid of a numerical simulation. Hydrogen liberation tests by conventional heating and microwaves were compared, showing that by microwave heating hydrogen release can be initiated and stopped in shorter times.2019-04-0

Release of Hydrogen from Nanoconfined Hydrides by Application of Microwaves

The release of hydrogen from solid hydrides by thermolysis can be improved by nanoconfinement of the hydride in a suitable micro/mesoporous support, but the slow heat transfer by conduction through the support can be a limitation. In this work, a C/SiO2 mesoporous material has been synthesized and employed as matrix for nanoconfinement of hydrides. The matrix showed high surface area and pore volume (386 m²/g and 1.41 cm³/g), which enabled the confinement of high concentrations of hydride. Furthermore, by modification of the proportion between C and SiO2, the dielectric properties of the complex could be modified, making it susceptible to microwave heating. As with this heating method the entire sample is heated simultaneously, the heat transfer resistances associated to conduction were eliminated. To demonstrate this possibility, ethane 1,2-diaminoborane (EDAB) was embedded on the C/SiO2 matrix at concentrations ranging from 11 to 31%wt using a wet impregnation method, and a device appropriate for hydrogen release from this material by application of microwaves was designed with the aid of a numerical simulation. Hydrogen liberation tests by conventional heating and microwaves were compared, showing that by microwave heating hydrogen release can be initiated and stopped in shorter times.2019-04-0

Novel windows for “solar commodities”: a device for CO2 reduction using plasmonic catalyst activation

Producción CientíficaA novel plasmonic reactor concept is proposed and tested to work as a visible energy harvesting device while allowing reactions to transform CO2 to be carried out. Particularly the reverse water gas shift (RWGS) reaction has been tested as a means to introduce renewable energy into the economy. The development of the new reactor concept involved the synthesis of a new composite capable of plasmonic activation with light, the development of an impregnation method to create a single catalyst reactor entity, and finally the assembly of a reaction system to test the reaction. The composite developed was based on a Cu/ZnO catalyst dispersed into transparent aerogels. This allows efficient light transmission and a high surface area for the catalyst. An effective yet simple impregnation method was developed that allowed introduction of the composites into glass microchannels. The activation of the reaction was made using LEDs that covered all the sides of the reactor allowing a high power delivery. The results of the reaction show a stable process capable of low temperature transformations

Strategies for GHG mitigation in Mediterranean cropping systems. A review

In this review we aimed to synthetize and analyze the most promising GHGs mitigation strategies for Mediterranean cropping systems. A description of most relevant measures, based on the best crop choice and management by farmers (i.e., agronomical practices), was firstly carried out. Many of these measures can be also efficient in other climatic regions, but here we provide particular results and discussion of their efficiencies for Mediterranean cropping systems. An integrated assessment of management practices on mitigating each component of the global warming potential (N2O and CH4 emissions and C sequestration) of production systems considering potential side-effects of their implementation allowed us to propose the best strategies to abate GHG emissions, while sustaining crop yields and mitigating other sources of environmental pollution (e.g. nitrate leaching and ammonia volatilization)

Treatment with tocilizumab or corticosteroids for COVID-19 patients with hyperinflammatory state: a multicentre cohort study (SAM-COVID-19)

Objectives: The objective of this study was to estimate the association between tocilizumab or corticosteroids and the risk of intubation or death in patients with coronavirus disease 19 (COVID-19) with a hyperinflammatory state according to clinical and laboratory parameters. Methods: A cohort study was performed in 60 Spanish hospitals including 778 patients with COVID-19 and clinical and laboratory data indicative of a hyperinflammatory state. Treatment was mainly with tocilizumab, an intermediate-high dose of corticosteroids (IHDC), a pulse dose of corticosteroids (PDC), combination therapy, or no treatment. Primary outcome was intubation or death; follow-up was 21 days. Propensity score-adjusted estimations using Cox regression (logistic regression if needed) were calculated. Propensity scores were used as confounders, matching variables and for the inverse probability of treatment weights (IPTWs). Results: In all, 88, 117, 78 and 151 patients treated with tocilizumab, IHDC, PDC, and combination therapy, respectively, were compared with 344 untreated patients. The primary endpoint occurred in 10 (11.4%), 27 (23.1%), 12 (15.4%), 40 (25.6%) and 69 (21.1%), respectively. The IPTW-based hazard ratios (odds ratio for combination therapy) for the primary endpoint were 0.32 (95%CI 0.22-0.47; p < 0.001) for tocilizumab, 0.82 (0.71-1.30; p 0.82) for IHDC, 0.61 (0.43-0.86; p 0.006) for PDC, and 1.17 (0.86-1.58; p 0.30) for combination therapy. Other applications of the propensity score provided similar results, but were not significant for PDC. Tocilizumab was also associated with lower hazard of death alone in IPTW analysis (0.07; 0.02-0.17; p < 0.001). Conclusions: Tocilizumab might be useful in COVID-19 patients with a hyperinflammatory state and should be prioritized for randomized trials in this situatio