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Scientific Papers in SCI



2020


Nanotecnología en Superficies y Plasma

Chemistry and Electrocatalytic Activity of Nanostructured Nickel Electrodes for Water Electrolysis

Lopez-Fernandez, E; Gil-Rostra, J; Espinos, JP; Gonzalez-Elipe, AR; Consuegra, AD; Yubero, F
ACS Catalysis, 10 (2020) 6159-6170

Herein we have developed nanostructured nickel-based electrode films for anion exchange membrane water electrolysis (AEMWE). The electrodes were prepared by magnetron sputtering (MS) in an oblique angle configuration and under various conditions aimed at preparing metallic, oxide, or oxyhydroxide films. Their electrochemical analysis has been complemented with a thorough physicochemical characterization to determine the effect of microstructure, chemical state, bilayer structure, and film thickness on the oxygen evolution reaction (OER). The maximum electrocatalytic activity was found for the metallic electrode, where analysis by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) demonstrated that the active catalytic phase at the surface after its electrochemical conditioning is a kind of oxidized nickel oxide/hydroxide layer with the thickness of a few nanometers. Electrochemical impedance spectroscopy analysis of these steady-state working electrodes supports that the enhanced performance of the metallic nickel anode vs other chemical states resides in the easier electron transfer through the electrode films and the various interlayers built up during their fabrication and activation. The long-term steady-state operation of the anodes and their efficiency for water splitting was proved in a full-cell AEMWE setup incorporating magnetron-sputtered metallic nickel as the cathode. This work proves that MS is a suitable technique to prepare active, stable, and low-cost electrodes for AEMWE and the capacity of this technique to control the chemical state of the electrocatalytically active layers involved in the OER.


June, 2020 | DOI: 10.1021/acscatal.0c00856

Química de Superficies y Catálisis

Reductant atmospheres during slow pyrolysis of cellulose: First approach to obtaining efficient char -based catalysts in one pot

Santos, JL; Centeno, MA; Odriozola, JA
Journal of Analytical and Applied Pyrolysis, 148 (2020) 104821

Char based metallic (Pd-Au-Ru-Pt/C) catalysts have drawn increasing research interest due to their versatility in biomass related industrial reactions. Recent studies dealing with the synthesis of char-based catalysts in one single step (one-pot) use reductant atmospheres for biomass pyrolysis. In this work, the influence of the use of a reductant N2/H2 atmosphere on the physicochemical properties of the resulting chars was evaluated in comparison with the use of an inert N2 atmosphere. Specifically, the fundamental parameter of the pyrolysis process, the temperature, was evaluated in the 500−900 °C range. Produced chars were fully characterized by N2 isotherms, ultimate CHNS analysis, X-ray Diffraction, Raman spectroscopy, Diffuse Reflectance Infrared spectroscopy, X-ray Photoelectron spectroscopy, helium Temperature Programmed Decomposition and Isoelectric Point analysis. Slow pyrolysis under reductant atmosphere favours deoxygenation reaction against dehydrogenation ones, reduces the carbon yield and results in chars with a more hydrophobic and graphitic character, higher thermal stability and weak surface functionalization. The use of intermediates temperatures (700 °C) favours the obtaining of chars with suitable physicochemical properties and good surface functionalization, which will facilitate the anchoring of the active phase on the surface, improving the metallic dispersion of the resulting one pot catalyst. This leads us to affirm that the use of reducing atmospheres at intermediate temperatures, is superior to the use of inert atmospheres for this purpose. This analysis on the impact of the use of a reductant atmosphere during slow pyrolysis of microcrystalline cellulose opens a new working path for the optimization of char-based catalysts obtained in a single stage.


June, 2020 | DOI: 10.1016/j.jaap.2020.104821

Fotocatálisis Heterogénea: Aplicaciones

Microwave-assisted sol-gel synthesis of TiO2 in the presence of halogenhydric acids. Characterization and photocatalytic activity

Puga,F.;Navío,J.A.;Jaramillo-Páez,C.;Sánchez-Cid,P.;Hidalgo,M.C.
Journal of Photochemistry and Photobiology A: Chemistry, 394 (2020) 112457

The synthesis of mesoporous TiO2 nanosheets is reported using Ti(IV) Isopropoxide as Ti(IV) precursor. A sol-gel process combined with microwave activation is used. Three different halogenhydric acids (HX), were used to peptise the sol: HF(ac), HCl (ac) and HBr (ac). The three obtained TiO2-I(HX) samples were characterized by XRD, XRF, N2-adsorption, SEM, TEM, DRS and XPS. The three synthesized samples have high values of specific surfaces (between 100 m2/g and 200 m2/g) and similar band gap values (3.2–3.3 eV). The analysis of the surface composition by XPS confirms the presence of the halogenated species (F, Cl or Br) on the surface of each ones of the samples. The nanometric size (ca 5 nm) of the particles for each of the three samples was confirmed by XRD and by TEM. On the other hand, the nature of the halogenated acid used plays a role in the composition of the phases. While the TiO2-I (HF) sample was 100 % anatase, the other samples turned out to be biphasic, showing anatase/rutile in the TiO2-I(HCl) sample and anatase/brookite in the TiO2-I(HBr) sample. The samples were tested under two illumination conditions (UV and visible light) using rhodamine B and caffeine. The indirect role of the halide agent on the photocatalytic activities thereof is discussed.


May, 2020 | DOI: 10.1016/j.jphotochem.2020.112457

Nanotecnología en Superficies y Plasma

Optical properties of molybdenum in the ultraviolet and extreme ultraviolet by reflection electron energy loss spectroscopy

Pauly, N; Yubero, F; Tougaard, S
Applied Optics, 59 (2020) 4527-4532

Optical properties of polycrystalline molybdenum are determined from ultraviolet up to extreme ultraviolet by reflection electron energy loss spectroscopy (REELS). Calculations are performed within the dielectric response theory by means of the quantitative analysis of electron energy losses at surfaces QUEELS-epsilon (k, omega)-REELS software [Surf. Interface Anal. 36, 824 (2004)] that allows the simulation of inelastic scattering cross sections, using a parametric energy loss function describing the optical response of the material. From this energy loss function, the real and imaginary parts of the dielectric function, the refractive index, and the extinction coefficient are deduced and compared with previously published results.


May, 2020 | DOI: 10.1364/AO.391014

Materiales Ópticos Multifuncionales

Premelting of ice adsorbed on a rock surface

Esteso, V; Palacios, SC; MacDowell, LG; Fiedler, J; Parsons, DF; Spallek, F; Miguez, H; Persson, C; Buhmann, SY; Brevik, I; Bostrom, M
Physical Chemistry Chemical Physics, 22 (2020) 11362-11373

Considering ice-premelting on a quartz rock surface (i.e. silica) we calculate the Lifshitz excess pressures in a four layer system with rock-ice-water-air. Our calculations give excess pressures across (1) ice layer, (2) water layer, and (3) ice-water interface for different ice and water layer thicknesses. We analyse equilibrium conditions where the different excess pressures take zero value, stabilized in part by repulsive Lifshitz interactions. In contrast to previous investigations which considered varying thickness of only one layer (ice or water), here we present theory allowing for simultaneous variation of both layer thicknesses. For a given total thickness of ice and water, this allows multiple alternative equilibrium solutions. Consequently the final state of a system will depend on initial conditions and may explain variation in experimental measurements of the thicknesses of water and ice layers.


May, 2020 | DOI: 10.1039/c9cp06836h

Química de Superficies y Catálisis

Time-resolved operando DRIFTS-MS study of the moisture tolerance of small-pore SAPO-34 molecular sieves during CH4/CO2 separation

Romero, M; Navarro, JC; Bobadilla, LF; Dominguez, MI; Ivanova, S; Romero-Sarria, F; Centeno, MA; Odriozola, JA
Microporous and Mesoporous Materials, 298 (2020) 110071

This study pretends to evaluate and understand the effect of moisture presence during CO2/CH4 separation on small-pore SAPO-34 molecular sieves. Two SAPO-34 samples with different physicochemical properties (composition, crystal size and texture) were prepared by hydrothermal synthesis using either one or a mixture of two templates. Transient operando DRIFTS-MS measurements revealed that the sample's hydrophobic character is associated to the presence of Si islands, which enhanced sample's moisture tolerance during repetitive adsorption/desorption cycles. This knowledge is fundamental to achieve the rational design of efficient SAPO-34 membranes under realistic conditions.


May, 2020 | DOI: 10.1016/j.micromeso.2020.110071

Materiales y Procesos Catalíticos de Interés Ambiental y Energético

Structural and surface considerations on Mo/ZSM-5 systems for methane dehydroaromatization reaction

Lopez-Martin, A; Caballero, A; Colon, G
Molecular Catalysis, 486 (2020) 110787

We have prepared a series of Mo/ZSM-5 systems by impregnation method with different metal loading. The optimum performance has been attained for 4% metal loading, yielding to ca. 2 mmol(benzene)/g(ca)(t) at the end of the reaction. The obtained catalysts were widely structural and surface characterized. As Mo content increases, the surface feature of the support is affected specially its mesoporosity. It has been stated the enormous complexity of Mo species present in the studied system. In situ characterization by XPS reveals different reduction and carburization behaviour depending on the Mo content.


May, 2020 | DOI: 10.1016/j.mcat.2020.110787

Materiales Ópticos Multifuncionales

Monitoring, Modeling, and Optimization of Lead Halide Perovskite Nanocrystal Growth within Porous Matrices

Tiede, DO; Rubino, A; Calvo, ME; Galisteo-Lopez, JF; Miguez, H
Journal of Physical Chemistry C, 124 (2020) 8041-8046

The growth of lead halide perovskites within metal-oxide nanoporous films has been recently considered as a means to obtain chemically and photostable ligand-free high-quality nanocrystals (NCs). The growth process, governed by the reactions taking place in nanoreactors dictated by the matrix pore size, has not been explored so far. In this work, we use photoluminescence as a tool to monitor the growth of perovskite NCs within the void network of an optically transparent matrix. We consider the effect of different external factors, such as temperature, light illumination, or precursor concentration, on the growth dynamics, and discuss a possible formation mechanism of the confined perovskite NCs. Based on this analysis, guidelines that could serve to improve the fabrication and optoelectronic quality of this type of NCs are also proposed.


April, 2020 | DOI: 10.1021/acs.jpcc.0c01750

Nanotecnología en Superficies y Plasma

Advanced Strategies in Thin Films Engineering by Magnetron Sputtering

Palmero, A; Martin, N
Coatings, 10 (2020) 419

This Special Issue contains a series of reviews and papers representing some recent results and some exciting perspectives focused on advanced strategies in thin films growth, thin films engineering by magnetron sputtering and related techniques. Innovative fundamental and applied research studies are then reported, emphasizing correlations between structuration process parameters, new ideas and approaches for thin films engineering and resulting properties of as-deposited coatings.


April, 2020 | DOI: 10.3390/coatings10040419

Materiales de Diseño para la Energía y Medioambiente

Bio-Based Coatings for Food Metal Packaging Inspired in Biopolyester Plant Cutin

Benitez, JJ; Osbild, S; Guzman-Puyol, S; Heredia, A; Heredia-Guerrero, JA
Polymers, 12 (2020) 942

Metals used for food canning such as aluminum (Al), chromium-coated tin-free steel (TFS) and electrochemically tin-plated steel (ETP) were coated with a 2-3-mu m-thick layer of polyaleuritate, the polyester resulting from the self-esterification of naturally-occurring 9,10,16-trihydroxyhexadecanoic (aleuritic) acid. The kinetic of the esterification was studied by FTIR spectroscopy; additionally, the catalytic activity of the surface layer of chromium oxide on TFS and, in particular, of tin oxide on ETP, was established. The texture, gloss and wettability of coatings were characterized by AFM, UV-Vis total reflectance and static water contact angle (WCA) measurements. The resistance of the coatings to solvents was also determined and related to the fraction of unreacted polyhydroxyacid. The occurrence of an oxidative diol cleavage reaction upon preparation in air induced a structural modification of the polyaleuritate layer and conferred upon it thermal stability and resistance to solvents. The promoting effect of the tin oxide layer in such an oxidative cleavage process fosters the potential of this methodology for the design of effective long-chain polyhydroxyester coatings on ETP.


April, 2020 | DOI: 10.3390/polym12040942

 

 

 

 

 

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