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Scientific Papers in SCI



2022


Reduction of N2O with hydrosilanes catalysed by RuSNS nanoparticles

Molinillo, P; Lacroix, B; Vattier, F; Rendon, N; Suarez, A; Lara, P
Chemical Communications

A series of RuSNS nanoparticles, prepared by decomposition of Ru(COD)(COT) with H-2 in the presence of an SNS ligand, have been found to catalyse the reduction of the greenhouse gas N2O to N-2 employing different hydrosilanes.


June, 2022 | DOI: 10.1039/d2cc01470j

Materiales Ópticos Multifuncionales

Effect of Spatial Inhomogeneity on Quantum Trapping

Esteso, V; Carretero-Palacios, S; Miguez, H
Journal of Physical Chemistry Letters, 13 (2022) 4513-4519

An object that is immersed in afluid and approaching a substrate mayfind apotential energy minimum at a certain distance due to the balance between attractive and repulsiveCasimir-Lifshitz forces, a phenomenon referred to as quantum trapping. This equilibriumdepends on the relative values of the dielectric functions of the materials involved. Herein, westudy quantum trapping effects in planar nanocomposite materials and demonstrate that they arestrongly dependent on the characteristics of the spatial inhomogeneity. As a model case, weconsider spherical particles embedded in an otherwise homogeneous material. We propose aneffective medium approximation that accounts for the effect of inclusions andfind that anunprecedented and counterintuitive intense repulsive Casimir-Lifshitz force arises as a result ofthe strong optical scattering and absorption size-dependent resonances caused by their presence. Our results imply that the properanalysis of quantum trapping effects requires comprehensive knowledge and a detailed description of the potential inhomogeneity(caused by imperfections, pores, inclusions, and density variations) present in the materials involved


June, 2022 | DOI: 10.1021/acs.jpclett.2c00807

Nanotecnología en Superficies y Plasma

Titania Enhanced Photocatalysis and Dye Giant Absorption in Nanoporous 1D Bragg Microcavities

Rico, VJ; Turk, H; Yubero, F; González-Elipe, AR
ACS Applied Nano Materials, 5 (2022) 5487-5497

Light trapping effects are known to boost the photocatalytic degradation of organic molecules in 3D photonic structures of anatase titania (a-TiO2) with an inverse opal configuration. In the present work, we show that photocatalytic activity can also be enhanced in a-TiO2 thin films if they are incorporated within a nanoporous 1D optical resonant microcavity. We have designed and manufactured multilayer systems that, presenting a high open porosity to enable a straightforward diffusion of photodegradable molecules, provide light confinement effects at wavelengths around the absorption edge of photoactive a-TiO2. In brief, we have observed that a nanoporous 1D Bragg microcavity prepared by electron beam evaporation at oblique angles comprising a central defect layer of nanoporous a-TiO2 boosts the photocatalytic degradation of nitrobenzene and methyl orange dye solutions. The multilayer structure of the microcavity was designed to ensure the appearance of optical resonances at the a-TiO2 layer location and wavelengths around the absorption onset of this semiconductor. In this porous 1D Bragg microcavity, the diffusion constraints of molecules through the capping layers covering the a-TiO2 are effectively compensated by an increase in the photocatalytic activity due to the light confinement phenomena. We also report that the absorption coefficient of methyl orange dye solution infiltrated within the pore structure of the microcavity is exalted at the wavelengths of the corresponding optical resonances. This effect gives rise to a small but non-negligible visible light photodegradation of dye molecules. The possibilities of tailoring the design of 1D photonic systems to boost the photocatalytic activity of a-TiO2 are discussed.


June, 2022 | DOI: 10.1021/acsanm.2c00477

Reactividad de Sólidos

Thermal behavior of ammonium fluorosilicates complexes: Obtaining and kinetic analysis

Resentera, AC; Perejon, A; Esquivel, MR; Perez-Maqueda, LA; Rodriguez, MH
Chemical Engineering Research amd Design, 182 (2022) 490-501

In this work, a mixture of (NH4)3SiF7/(NH4)2SiF6 powders was obtained as a by-product of the Li extraction process from alpha-spodumene aluminosilicate with NH4HF2. The thermal behavior of the powders was analyzed by non-isothermal thermogravimetric experiments. The kinetic parameters that describe the processes involved were obtained using mathematical deconvolution, Friedman's method, combined kinetic analysis, and nonlinear regression optimization. The results show that the process occurs in two partially overlapping steps, the thermal decomposition of (NH4)3SiF7 into (NH4)2SiF6 and the subsequent sublimation of (NH4)2SiF6. The apparent activation energies were 72.6 and 79.8 kJ/ mol for steps 1 and 2, respectively. The apparent pre-exponential factors were 1.19 x 106 and 2.50 x 105 s-1, respectively. The kinetic models indicated that Step 1 follows an A2 model, while Step 2 follows an F0 model. Finally, the resulting kinetic parameters allowed the reconstruction of the original experimental curves and obtaining predictions of curves recorded under other heating programs.


June, 2022 | DOI: 10.1016/j.cherd.2022.04.021

Materiales Avanzados

Thermal behaviour of the different parts of almond shells as waste biomass

Garzon, E; Arce, C; Callejon-Ferre, AJ; Perez-Falcon, JM; Sanchez-Soto, PJ
Journal of Thermal Analysis and Calorimetry, 147 (2022) 5023-5035

The main aim of this study is to investigate the thermal behaviour of the different parts of almond shells produced in an almond industry as a waste biomass. For this purpose, several experiments have been conducted under laboratory conditions. After removing the mature almonds, the waste raw materials subject of this study were treated with distilled water (10 min) and separated in several parts. Taking into account their physical characteristics, they were: (a) complete shells: exocarp, mesocarp and endocarp without grinding (Sample C); (b) ground samples of complete shells, sieved under 0.2 mm (Sample M); (c) hard layers of the endocarp (Sample E); (d) internal layers of the endocarp (Sample I); and (e) mature drupes (Sample P) or skin, being constituted by the flexible part of green colour (fresh form) or yellow (after drying). The thermal behaviour of all these sample materials has been investigated using a laboratory furnace, with determination of ash contents and mass loss by progressive heating (120 min of holding time). Elemental and DTA-TG/DTG analyses of selected sample materials have been carried out. Although a complete study can be very complex, a first approach has been performed in this investigation. Results on thermal decomposition of this biomass waste have been presented to emphasize the main differences between sample materials of almond shells. These results have demonstrated the influence of several parameters, such as the particle size, and previous treatments in the thermal behaviour of the different parts of the almond shells, as showed in this investigation. Structural analysis of almond shells allowed to determine lignin, cellulose and hemicellulose. From the lignin content, it has been predicted the higher heating value (18.24 MJkg(-1)) of this waste as by-product of industrial interest. Other linear correlations to calculate this parameter have been applied with similar results in all these samples.


June, 2022 | DOI: 10.1007/s10973-021-10940-x

Nanotecnología en Superficies y Plasma

Electron beam evaporated vs. magnetron sputtered nanocolumnar porous stainless steel: Corrosion resistance, wetting behavior and anti-bacterial activity

Bobaru, S; Rico-Gavira, V; Garcia-Valenzuela, A; Lopez-Santos, C; Gonzalez-Elipe, AR
Materials Today Communications, 31 (2022) 103266

Stainless steel (SS), widely used because of its outstanding corrosion protection properties, does not possess any particular anti-stain or anti-bacterial activity as required for household and sanitary applications. This work reports the fabrication of SS thin films that, keeping a similar corrosion resistance than the bulk material, presents hydrophobicity and anti-bacterial activity. These thin films are prepared at ambient temperature by physical vapor deposition (PVD), either electron beam evaporation (EBE) or magnetron sputtering (MS), at oblique angles (OAD). According to their scanning electron microcopy and atomic force microscopy analysis, the microstructure of the OAD-SS thin films consisted of tilted and separated nanocolumns defining a surface topology that, characterized by a high percentage of void space, varied with the deposition conditions and procedure, either EBE or MS. It has been shown that particularly the nanocolumnar MS-OAD thin films preserved and even improved the high corrosion resistance of compact SS, as determined by electrochemical analysis. Besides, all OAD-SS thin films depict hydrophobicity and a high antibacterial activity. These features, particularly remarkable for the MS-OAD thin films, have been related with their tip-like termination at the surface and the existence of large void spaces separating the nanocolumns. This topology appears to affect negatively the bacteria's deployment onto the surface and therefore the survival rate. Differences in the corrosion and antibacterial performance between EBE and MS-OAD thin films have been related with the specificities of these two PVD methods of thin film preparation. A relatively high abrasion resistance, as determined by abrasion tests, supports the use of MS-OAD thin films for the protection of commodity materials.


June, 2022 | DOI: 10.1016/j.mtcomm.2022.103266

Nanotecnología en Superficies y Plasma

Comparative analysis of the germination of barley seeds subjected to drying, hydrogen peroxide, or oxidative air plasma treatments

Perea-Brenes, A; Gomez-Ramirez, A; Lopez-Santos, C; Oliva-Ramirez, M; Molina, R; Cotrino, J; García, JL; Cantos, M; González-Elipe, ARA
Plasma Processes and Polymers 19 (2022) e2200035

Acceleration in germination time by 12-24 h for barley seeds treated with atmospheric air plasmas may have a significant economic impact on malting processes. In this study, the increase in germination rate and decrease in contamination level upon plasma treatment could not be directly correlated with any significant increase in the water uptake capacity, except for seeds exposed to mild drying treatment. A variety of germination essays have been carried out with seeds impregnated with an abscisic acid solution, a retarding factor of germination, treated with a peroxide solution, and/or subjected to the plasma and drying treatments. Results suggest that plasma and hydrogen peroxide treatments induce the formation of reactive oxygen and nitrogen species that affects the abscisic acid factor and accelerate the germination rate.


June, 2022 | DOI: 10.1002/ppap.202200035

Nanotecnología en Superficies y Plasma

Nanostructured nickel based electrocatalysts for hybrid ethanol-water anion exchange membrane electrolysis

Lopez-Fernandez, E; Gomez-Sacedon, C; Gil-Rostra, J; Espinos, JP; Gonzalez-Elipe, AR; Yubero, F
Journal of Environmental Chemical Engineering, 10 (2022) 107994

Ni and Ni-Fe nanostructured layers prepared by magnetron sputtering in an oblique angle deposition configuration (MS-OAD) have been used as anode and cathode catalysts for hybrid ethanol-water electrolysis in an anion exchange membrane (AEM) electrolyser. Physico-chemical and electrochemical characterization in a threeelectrode cell has been carried out to determine the optimal characteristics of the anodic films. Current densities up to 434 mA cm-2 at 2.0 V in a 1.5 M EtOH and 2.0 M KOH fuel solution were achieved with excellent operational stability for 3 days. These experiments show that the oxygen evolution reaction taking place at the anode is completely replaced by the ethanol oxidation reaction under our explored reaction conditions. The obtained results evidence the interest of this kind of organic vs. pure water electrolysis to decrease the overall electrical energy consumption for the production of hydrogen.


June, 2022 | DOI: 10.1016/j.jece.2022.107994

Fotocatálisis Heterogénea: Aplicaciones

Pursuing efficient systems for glucose transformation to levulinic acid: Homogeneous vs. heterogeneous catalysts and the effect of their co-action

Bounoukta, CE; Megias-Sayago, C; Ivanova, S; Ammari, F; Centeno, MA; Odriozola, JA
FUEL, 318 (2022) 123712

Exploring available catalytic systems to understand their behavior is a must to properly design efficient catalysts aiming to definitively drive biomass from laboratory to industrial scale. Glucose transformation to levulinic acid involves cascade reactions with specific requirements, different active sites in each case and secondary reactions hard to avoid which are intrinsically linked to the catalyst's nature and reaction conditions. In the present work, homogeneous, heterogeneous and heterogeneous/homogeneous catalysts are considered with the unique goal of improving levulinic acid yield while understanding the catalytic behaviour of cost-effective catalysts. The choice of the catalytic systems and the effect of the main reaction parameters on activity and selectivity is studied and discussed.


June, 2022 | DOI: 10.1016/j.fuel.2022.123712

Materiales Avanzados

Vitrification rate and estimation of the optimum firing conditions of ceramic materials from raw clays: A review

Garzon, E; Perez-Villarejo, L; Eliche-Quesada, D; Martinez-Martinez, S; Sanchez-Soto, PJ
Ceramics International, 48 (2022) 15889-15898

The present work is a review concerning the previous investigations on the vitrification behaviour of clays containing kaolinite, feldspars, muscovite (illite/sericite) and pyrophyllite. These clays are silico-aluminous and have interesting properties as raw materials for structural ceramics. The mineralogical and chemical composition were determined. Then, the vitrification in these clay samples using pressed bodies was investigated by few researchers in the temperature range 800-1350 degrees C with 0.5-5.5 h of soaking times. The effect of heat treatments on the degree of vitrification in these clays was characterized by bulk densities of the ceramic bodies at the fired stage. It was found some variations of bulk density values for all these clays fired in the range 1000-1150 degrees C, with marked decreases of the values obtained at 1200 degrees C and 1300 degrees C. A first order reaction kinetics was applied to the analysis of vitrification of the ceramic bodies under isothermal heating. The method is based on experi-mental data of bulk densities, being proposed for the estimation of the relative degree of vitrification resulting from different firing schedules. The analysis considered the temperature dependence of the rate of vitrification following Arrhenius behaviour. Thus, the vitrification activation energy can be obtained. The activation energies for the physical process of vitrification in these clays ranged from 45 to 151 kJ/mol. The relative rates of vitrification or degree of vitrification attained during heating and soaking were calculated. The results suggested that the contribution of vitrification due to heating in all these clays was relatively small compared to the vitrification during soaking. However, it was evidenced that the influence of the particle sizes in the thermal behaviour of these clays cannot be neglected. The vitrification rate equations, as deduced in these previous studies, can be useful tools to estimate the optimum firing conditions of these clays, allowing the extension of this method to other clay types.


June, 2022 | DOI: 10.1016/j.ceramint.2022.02.129

 

 

 

 

 

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