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SiOx by magnetron sputtered revisited: Tailoring the photonic properties of multilayers

Garcia-Valenzuela, A; Alvarez, R; Espinos, JP; Rico, V; Gil-Rostra, J; Palmero, A; Gonzalez-Elipe, AR
Applied Surface Science, 488 (2019) 791-800


Traditionally porous silicon based photonic structures have been prepared by electrochemically etching of silicon. In this work, porous multilayers of nanocolumnar SiOx and SiO2 thin films acting as near infrared (NIR) 1D-photonic nanostructures are prepared by magnetron sputtering deposition at oblique angles (MS-OA). Simultaneous control of porosity and stoichiometry of the stacked films is achieved by adjusting the deposition angle and oxygen partial pressure according to a parametric formula. This new methodologoy is proved for the synthesis of SiOx thin films with x close to 0.4, 0.8, 1.2, 1.6 and nanostructures varying from compact (at 0 degrees deposition angle) to highly porous and nanocolumnar (at 70 degrees and 85 degrees deposition angles). The strict control of composition, structure and nanostructure provided by this technique permits a fine tuning of the absorption edge and refraction index at 1500 nm of the porous films and their manufacturing in the form of SiOx-SiO2 porous multilayers acting as near infrared (NIR) 1D-photonic structures with well-defined optofluidic responses. Liquid tunable NIR Bragg mirrors and Bragg microcavities for liquid sensing applications are presented as proof of concept of the possibilities of this MS-OA manufacturing method as an alternative to the conventional electrochemical fabrication of silicon based photonic structures.

September, 2019 | DOI: 10.1016/j.apsusc.2019.05.273

Extraordinary visible photocatalytic activity of a Co0.2Zn0.8O system studied in the Remazol BB oxidation

KarimTanji; J.A.Navio; Jamal Naja; M.C.Hidalgo; Abdellah Chaqroune; C.Jaramillo-Páez; Abdelhak Kherbeche
Journal of Photochemistry and Photobiology A: Chemistry, 382 (2019) 111877


Nanoparticles of CoxZn1-xO system with a nominal composition of x=0.2 were synthesized by the Solution Combustion Method (SCM). Structural and morphological studies as well as the chemical composition of the material were widely investigated by different techniques. Photocatalytic activity under UV and Visible illumination was studied by means of the Remazol Brilliant Blue dye (RBB) oxidation reaction. The effect of different experimental parameters, such as the initial dye concentration, photocatalyst mass, pH or hydrogen peroxide concentration on the RBB discoloration under UV irradiation was studied. Optimal experimental conditions were found to be a photocatalyst mass of 1 g.L-1, dye concentration of 20 mg.L-1 and solution pH of 11. Hydrogen peroxide addition was found to have no effect in the photocatalytic behavior of the material in the range of concentration studied (0 to 6•10-4 M). The optimal parameters were chosen to investigate the degradation of RBB under UV-illumination and just visible illumination. It was observed that the UV-photocatalytic property of pristine ZnO for the RBB removal was scarcely improved after cobalt-incorporation, whereas the effect of cobalt incorporation into ZnO greatly enhanced the RBB conversion under visible illumination. Even more interesting is that, under same experimental conditions, the visible efficiency of the Co-ZnO system is the same that the one showed under UV illumination, i.e. the system does not loose efficiency when illuminated only with visible light.

September, 2019 | DOI: 10.1016/j.jphotochem.2019.111877

Support effects on NiO-based catalysts for the oxidative dehydrogenation (ODH) of ethane

Delgado, D; Sanchis, R; Cecilia, JA; Rodriguez-Castellon, E; Caballero, A; Solsona, B; Nieto, JML
Catalysis Today, 333 (2019) 10-16


We report on the effect of NiO-support interactions on the chemical nature of Ni species in a series of supported NiO catalysts for the ODH of ethane. SiO2, TiO2-anatase, a high surface area TiO2 and a porous clay hetero-structure (PCH) with TiO2 and SiO2 pillars were used as supports, which led to a selectivity to ethylene in the range 30-90% over supported NiO catalysts. The catalysts were characterized by means of XRD, N-2-Adsorption, H-2-TPR, XPS and in situ (under H-2 reductive atmosphere) and ex situ XAS spectroscopy. The catalytic performance of supported materials is discussed in terms of their reducibility and specific reduction kinetics, but also taking into account the specific chemical nature of Ni species on each catalyst. The influence of the particle size and the presence of Ni and O vacancies on the catalytic performance in the ODH of ethane is inferred.

August, 2019 | DOI: 10.1016/j.cattod.2018.07.010

Au/Al2O3 - Efficient catalyst for 5-hydroxymethylfurfural oxidation to 2,5-furandicarboxylic acid

Megias-Sayago, C; Lolli, A; Ivanova, S; Albonetti, S; Cavani, F; Odriozola, JA
Catalysis Today, 333 (2019) 169-175


The catalytic activity of a simple Au/Al2O3 catalytic system prepared by the direct anionic exchange (DAE) method was evaluated in the selective 5-hydroxymethylfurfural (HMF) oxidation under mild conditions, using molecular oxygen as the oxidant. The influence of the HMF/NaOH ratio and reaction time on product yield and distribution were studied and discussed in detail. Extremely high activity and selectivity were observed in mild conditions, with 99% of 2,5-furandicarboxylic acid (FDCA) production at full HMF conversion after 4 h with the use of only 4 equivalents of NaOH at 70 degrees C. Catalyst viability and stability were verified by repeating the cycle up to five times. Changes in the nature of the support were also contemplated by introducing some ceria fraction, i.e. 20 wt%.

August, 2019 | DOI: 10.1016/j.cattod.2018.04.024

Mechanically induced combustion synthesis and thermoelectric properties of nanostructured strontium hexaboride (SrB6)

Jalaly, M; Khosroshahi, BK; Gotor, FJ; Sayagues, MJ; Yamini, SA; Failamani, F; Mori, T
Ceramics International, 45 (2019) 14426-14431


The nanoparticles of strontium hexaboride (SrB6) were synthesized by a mechanically induced magnesiothermic combustion in the Mg/B2O3/SrO system. Ignition time in this system was recorded to be 23 min of milling. X-ray diffraction(XRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM) techniques were used to characterize the combustion product. Thermal analysis was employed to assess the formation mechanism. It was revealed that Mg initially reduced B2O3 in a combustive manner to generate elemental boron and a large amount of heat, resulting in the reduction of SrO by Mg at high temperature. The in-situ formed elemental Sr and B react immediately to generate SrB6. Thermoelectric properties of consolidated SrB6, including thermal conductivity, Seebeck coefficient, electrical conductivity, and figure-of-merit were evaluated at the temperature range of 300–873 K.

August, 2019 | DOI: 10.1016/j.ceramint.2019.04.163

Natural abundance O-17 MAS NMR and DFT simulations: New insights into the atomic structure of designed micas

Pavon, E; Osuna, FJ; Alba, MD; Delevoye, L
Solid State Nuclear Magnetic Resonance, 100 (2019) 45-51


Combining O-17 Magic-Angle Spinning (MAS) NMR at natural abundance with DFT calculations is a promising methodology to shed light on the structure and disorder in tetrahedral sheets of designed micas with enhanced properties. Among brittle micas, synthetic mica is an important alternative to natural ones with a swelling sheet-like structure that results in many applications, by exploiting unique characteristics. Lowenstein's rule is one of the main chemical factor that determines the atomic structure of aluminosilicates and furthermore their properties. In the present article, O-17 MAS NMR spectroscopy is used to validate (or not) the agreement of the Lowenstein's rule with the distribution of Si and Al sites in the tetrahedral sheets of synthetic micas. O-17 MAS spectra of synthetic high-charged micas exhibit two regions of signals that revealed two distinguishable oxygen environments, namely Si-O-X (with X = Si, Al-tet , Mg) and Al-tet -O-Y (Y=Mg or Al-tet). DFT calculations were also conducted to obtain the O-17 chemical shift and other NMR features like the quadrupolar coupling constant, C-Q, for all of the oxygen environments encountered in the two model structures, one respecting the Lowenstein's rule and the other involving Al-tet -O-Al-tet and Si-O-Si environments. Our DFT calculations support the O-17 assignment, by confirming that Al-tet -O-3Mg and Al tet -O-Al tet oxygen environments show chemical shifts under 30 ppm and more important, with quadrupolar coupling constants of about 1 MHz, in line with the spectral observation. By quantifying the O-17 MAS NMR spectra at natural abundance, we demonstrate that one of the synthetic mica compositions does not meet the Lowenstein's rule.

August, 2019 | DOI: 10.1016/j.ssnmr.2019.03.006

Structural and compositional analysis of Co-based coatings after catalytic tests for the sodium borohydride hydrolysis

Beltran, AM
Materials Research Express, 6 (2019) art. 085511


The use of Co-based catalysts for the sodium borohydride hydrolysis for hydrogen production is a well-known process as a source of clean energy, although its mechanisms are still under discussion. With the aim of acquiring a deeper knowledge about this catalytic process, three different catalysts (Co, CoC and CoB) were deposited as a thin film layer by magnetron sputtering onto a polymeric membrane, used as a substrate and analyzed by advance transmission and scanning-transmission electron microscopy techniques (STEM). Structural and compositional characterizations, by electron energy loss spectroscopy (EELS), have been performed on the coatings before and after their use as catalysts on the sodium borohydride reaction for 90 min, to check the production of hydrogen. Results have shown the formation of CoxB nanoflakes and other Co-based compounds over the catalysts and related to their catalytic activity. Knowing the changes in the structure and composition of the catalysts is key to understanding their catalytic behavior, activity and durability. Among the analyzed catalysts, the Co-C presents better activity during the first cycles, which is related to a larger formation of CoxB.

August, 2019 | DOI: 10.1088/2053-1591/ab1e27

Au/CeO2-ZnO/Al2O3 as Versatile Catalysts for Oxidation Reactions: Application in Gas/Liquid Environmental Processes

Megias-Sayago, C; Reina, TR; Ivanova, S; Odriozola, JA
Frontiers in Chemistry, 7 (2019) art. 504


The present work showcases the versatility of nanogold systems supported on Zn-doped ceria when applied in two important environmental processes, the total CO oxidation, and the liquid phase oxidation of glucose to gluconic acid. In the CO oxidation the suitability of these materials is clearly demonstrated achieving full conversions even at sub-ambient conditions. Regarding the glucose oxidation our materials display high conversion values (always over 50%) and very importantly full or almost full selectivity toward gluconic acid-an added value platform chemical in the context of biomass upgrading routes. The key factors controlling the successful performance on both reactions are carefully discussed and compared to previous studies in literature. To our knowledge this is one of the very few works in catalysis by gold combining liquid and gas phase reactions and represents a step forward in the flexible behavior of nano gold catalysts.

July, 2019 | DOI: 10.3389/fchem.2019.00504

Large gap atmospheric pressure barrier discharges using ferroelectric materials

Navascues, P.; Gonzalez-Elipe, A. R.; Cotrino, J.; Gomez-Ramirez, A.
Plasma Sources Sciences & Tecnology,


Bionanocomposites based on chitosan intercalation in designed swelling high-charged micas

Alba, MD; Cota, A; Osuna, FJ; Pavon, E; Perdigon, AC; Raffin, F
Scientific Reports, 9 (2019) art. 10265


Bionanocomposites based on layered inorganic components, as clays, and polymers of biological origin, as chitosan, have a major impact in medical and environmental fields, being economical and environmentally friendly materials. Na-Mn micas (n = 2 and 4) with controlled surface charge, high cation exchange capacity and swelling behaviour, are attractive inorganic composite components that exhibit improved adsorption properties compared to other inorganic solids which makes them potentially useful for bionanocomposites. The goal of this research was to explore the potential use of those synthetic brittle micas to form eco-friendly bionanocomposites with chitosan biopolymer. Hence, chitosan-mica bionanocomposites were prepared by ion-exchange reaction between chitosan solution and synthetic high charge mica. X-ray diffraction, Fourier transform infrared spectroscopy, thermal analysis, MAS-NMR spectroscopy and zeta-potential have been employed for bionanocomposites characterization. The results showed that the adsorption of chitosan is effective, although a chitosan portion remains in the outer surface being hydrogen-bonded to the tetrahedral sheet of the silicate.

July, 2019 | DOI: 10.1038/s41598-019-46495-z

Size-tailored Ru nanoparticles deposited over gamma-Al2O3 for the CO2 methanation reaction

Navarro-Jaen, S; Navarro, JC; Bobadilla, LF; Centeno, MA; Laguna, OH; Odriozola, JA
Applied Surface Science, 483 (2019) 750-761


By means of the polyol method, a series of 5 wt% Ru/Al2O3 catalysts was synthesized controlling the particle size of the ruthenium species. The physico-chemical characterization demonstrated the successful particle size control of the Ru species, in such a way that higher the Ru/PVP ratio, higher the Ru particle size. Moreover, there are evidences that suggest preferential growth of the RuO2 clusters depending on the Ru/PVP ratio. Regarding the catalytic activity during the CO2 methanation, the total conversion and the CH4 yield increased with the particle size of Ru. Nevertheless, a considerable enhancement of the catalytic performance of the most active system was evidenced at 4 bar, demonstrating the improvement of the thermodynamics (superior total conversion) and kinetics (superior reaction rate) of the CO2 methanation at pressures above the atmospheric one. Finally, the in situ DRIFTS study allowed to establish that CO2 was dissociated to CO* and O* species on the metallic Ru particles, followed by the consecutive hydrogenation of CO* towards CHO*, CH2O*, CH3O*, and finally CH4 molecules, which were further desorbed from the catalyst. Thus from the mechanistic point of view, a suitable particle size of the Ru nanoparticles along with the high-pressure effects results in the enhancement of the availability of hydrogen and consequently in the formation of CHxO species that enhance the cleavage of the C-O bond, which is the rate-determining step of the overall CO2 methanation process.

July, 2019 | DOI: 10.1016/j.apsusc.2019.03.248

Plasma Enabled Conformal and Damage Free Encapsulation of Fragile Molecular Matter: from Surface-Supported to On-Device Nanostructures

Alcaire, M; Aparicio, FJ; Obrero, J; Lopez-Santos, C; Garcia-Garcia, FJ; Sanchez-Valencia, JR; Frutos, F; Ostrikov, K; Borras, A; Barranco, A
Advanced Functional Materials, (2019) art. 1903535


Damage-free encapsulation of molecular structures with functional nanolayers is crucial to protect nanodevices from environmental exposure. With nanoscale electronic, optoelectronic, photonic, sensing, and other nanodevices based on atomically thin and fragile organic matter shrinking in size, it becomes increasingly challenging to develop nanoencapsulation that is simultaneously conformal at atomic scale and does not damage fragile molecular networks, while delivering added device functionality. This work presents an effective, plasma-enabled, potentially universal approach to produce highly conformal multifunctional organic films to encapsulate atomically thin graphene layers and metalorganic nanowires, without affecting their molecular structure and atomic bonding. Deposition of adamantane precursor and gentle remote plasma chemical vapor deposition are synergized to assemble molecular fragments and cage-like building blocks and completely encapsulate not only the molecular structures, but also the growth substrates and device elements upon nanowire integration. The films are insulating, transparent, and conformal at sub-nanometer scale even on near-tip high-curvature areas of high-aspect-ratio nanowires. The encapsulated structures are multifunctional and provide effective electric isolation, chemical and environmental protection, and transparency in the near-UV-visible-near-infrared range. This single-step, solvent-free remote-plasma approach preserves and guides molecular building blocks thus opening new avenues for precise, atomically conformal nanofabrication of fragile nanoscale matter with multiple functionalities.

July, 2019 | DOI: 10.1002/adfm.201903535

2D compositional self-patterning in magnetron sputtered thin films

Garcia-Valenzuela, A; Alvarez, R; Rico, V; Espinos, JP; Lopez-Santos, MC; Solis, J; Siegel, J; del Campo, A; Palmero, A; Gonzalez-Elipe, AR
Applied Surface Science, 480 (2019) 115-121


Unlike topography patterning, widely used for numerous applications and produced by means of different technologies, there are no simple procedures to achieve surface compositional patterning at nanometric scales. In this work we have developed a simple method for 2D patterning the composition of thin films. The method relies on the magnetron sputtering deposition at oblique angles onto patterned substrates made by laser induced periodic surface structures (LIPSS). The method feasibility has been demonstrated by depositing SiOx thin films onto LIPSS structures generated in Cr layers. A heterogeneous and aligned distribution of O/Si ratios (and different Sin+ chemical states) along the LIPSS structure in length scales of some hundreds nm's has been proven by angle resolved X-ray photoelectron spectroscopy and a patterned arrangement of composition monitored by atomic force microscopy-Raman analysis. The obtained results are explained by the predictions of a Monte Carlo simulation of this deposition process and open the way for the tailored one-step fabrication of surface devices with patterned compositions.

June, 2019 | DOI: 10.1016/j.apsusc.2019.02.206

Comprehensive Experimental and Theoretical Study of the CO plus NO Reaction Catalyzed by Au/Ni Nanoparticles

Kyriakou, G; Marquez, AM; Holgado, JP; Taylor, MJ; Wheatley, AEH; Mehta, JP; Sanz, JF; Beaumont, SK; Lambert, RM
ACS Catalysis, 9 (2019) 4919-4929


The catalytic and structural properties of five different nanoparticle catalysts with varying Au/Ni composition were studied by six different methods, including in situ X-ray absorption spectroscopy and density functional theory (DFT) calculations. The as-prepared materials contained substantial amounts of residual capping agent arising from the commonly used synthetic procedure. Thorough removal of this material by oxidation was essential for the acquisition of valid catalytic data. All catalysts were highly selective toward N-2 formation, with 50-50 Au:Ni material being best of all. In situ X-ray absorption near edge structure spectroscopy showed that although Au acted to moderate the oxidation state of Ni, there was no clear correlation between catalytic activity and nickel oxidation state. However, in situ extended X-ray absorption fine structure spectroscopy showed a good correlation between Au Ni coordination number (highest for Ni50Au50) and catalytic activity. Importantly, these measurements also demonstrated substantial and reversible Au/Ni intermixing as a function of temperature between 550 degrees C (reaction temperature) and 150 degrees C, underlining the importance of in situ methods to the correct interpretation of reaction data. DFT calculations on smooth, stepped, monometallic and bimetallic surfaces showed that N + N recombination rather than NO dissociation was always rate-determining and that the activation barrier to recombination reaction decreased with increased Au content, thus accounting for the experimental observations. Across the entire composition range, the oxidation state of Ni did not correlate with activity, in disagreement with earlier work, and theory showed that NiO itself should be catalytically inert. Au-Ni interactions were of paramount importance in promoting N + N recombination, the rate-limiting step.

June, 2019 | DOI: 10.1021/acscatal.8b05154

Exchange bias and two steps magnetization reversal in porous Co/CoO layer

Ovejero, JG; Godinho, V; Lacroix, B; Garcia, MA; Hernando, A; Fernandez, A
Materials & Design, 171 (2019) 107691


In this paper Co/CoO thick layers (hundreds of nanometers) of different porosity and oxidation degree were prepared in a magnetron sputtering deposition processby tailoring the DC sputtering power, as well as the process gas and target composition. The control of the synthesis parameters allowed the nanostructuration of the films with a singular distribution of closed pores and a controlled amount of CoO. We observed an exchange bias field of 2.8 KOe for porous Co/CoO composites, similar to Co/CoO bilayers but for coatings thicker than 300 nm. Besides, it was observed that the coating presents bistable magnetic features when cooled under zero field conditions as a result of the unusual exchange coupling.

June, 2019 | DOI: 10.1016/j.matdes.2019.107691

Microbiological induced carbonate (CaCO3) precipitation using clay phyllites to replace chemical stabilizers (cement or lime)

Morales, L; Garzon, E; Romero, E; Sanchez-Soto, PJ
Applied Clay Science, 174 (2019) 15-28


The objective of the present study is to develop a biotechnological tool for a new application of clay phyllites as stabilized materials in linear works replacing chemical stabilizer (e.g. cement or lime) by natural cement, formed by precipitated calcium carbonate generated by microorganisms of the Bacillaceae family (Bacilluspasteurii). Part of the development process conducting a chemical and mineralogical characterization and an examination of physical and hydromechanical properties. The results of this study show that the effect of bacteria on clay phyllites increases the calcium carbonate content, specific surface area and plasticity values. These increased values are caused by the addition of a non-plastic component to clay phyllites resulting in a more aggregated structure through the precipitation of calcium carbonate from the bacteria, ultimately filling the pores of this material. Microbiological treatments on clay phyllites tends to aggregate the original particles, creating aggregates that are partially associated with the formation of calcium carbonate. Said process is influenced by the curing and compaction procedures conducted on samples, which also cause breakage of carbonated structures formed during treatment. As a result of this breaking process of aggregates, some compaction energy is lost and the treated samples do not reach the maximum dry density of the natural state for the same level of compaction energy applied. Treated samples display a slightly larger friction angle with no cohesion, consistent with filling properties and denser condition. Compressibility is consistently lower than that of the natural state. Comparison of collapse data showsthat the occurrence and amount of collapse are controlled by the as-compacted dry density. It is also determined that higher compaction effort is even more effective than increasing the amount of bacteria introduced to stabilize the sample for the filling of pores (size ranges 3–50 μm) with calcium carbonate. However, the post-ageing compaction destroys the initial binding/cementation effect.

June, 2019 | DOI: 10.1016/j.clay.2019.03.018

Preparation, characterization and photocatalytic degradation of Rhodamine B dye over a novel Zn3(PO4)2/BiPO4 catalyst

Naciri,Y.;Chennah,A.;Jaramillo-Páez,C.;Navío,J.A.;Bakiz, B.;Taoufyq,A.;Ezahri,M.;Villain,S.;Guinneton,F.;Benlhachemi,A.
Journal of Environmental Chemical Engineering, 7 (2019) 103075


In this work, a facile method was used to synthesize the Zn3(PO4)2/BiPO4 composite photocatalysts with different Bi contents followed by heat treatment at 900 °C for 3 h. The as-prepared samples were studied by a variety of characterization techniques including X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) combined with energy dispersive X-ray diffraction (EDX), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV–vis diffuse reflectance spectroscopy (DRS). The UV–vis spectroscopy was used to analyze the evolution of Rhodamine B discoloration in presence of the synthesized phosphate photocatalysts. The XRD, SEM-EDX, TEM, DRS and XPS analyses confirmed the formation of heterojunction structure between both materials, during the process of co-precipitation and ulterior heat treatment. The photocatalytic tests showed that photocatalytic ability of the 70% Bi-Zn3(PO4)2 composites was higher than that of pure Zn3(PO4)2 and BiPO4 after 1 h of UV-illumination. The obviously enhanced photocatalytic activity of the 70% Bi-Zn3(PO4)2 sample could be mainly attributed to the formation of the heterojunction, accelerating the separation of photogenerated charge carriers. A plausible mechanism of the photocatalytic degradation of RhB on Zn3(PO4)2/BiPO4 composites is proposed. The reduction in the Chemical Oxygen Demand (COD) revealed the mineralization of dye along with color removal. Thus, it can be suggested that the 70% Bi-Zn3(PO4)2 can serve as a promising photocatalyst in the degradation of organic contaminants under UV light.

June, 2019 | DOI: 10.1016/j.jece.2019.103075

Multifunctional antimicrobial chlorhexidine polymers by remote plasma assisted vacuum deposition

Mora-Boza, A; Aparicio, FJ; Alcaire, M; Lopez-Santos, C; Espinos, JP; Torres-Lagares, D; Borras, A; Barranco, A
Frontiers of chemical science and engineering, 13 (2019) 330-339


Novel antibacterial materials for implants and medical instruments are essential to develop practical strategies to stop the spread of healthcare associated infections. This study presents the synthesis of multifunctional antibacterial nanocoatings on polydimethylsiloxane (PDMS) by remote plasma assisted deposition of sublimated chlorhexidine powders at low pressure and room temperature. The obtained materials present effective antibacterial activity against Escherichia coli K12, either by contact killing and antibacterial adhesion or by biocide agents release depending on the synthetic parameters. In addition, these multifunctional coatings allow the endure hydrophilization of the hydrophobic PDMS surface, thereby improving their biocompatibility. Importantly, cell-viability tests conducted on these materials also prove their non-cytotoxicity, opening a way for the integration of this type of functional plasma films in biomedical devices.

June, 2019 | DOI: 10.1007/s11705-019-1803-6

Surface nickel particles generated by exsolution from a perovskite structure

Aguero, FN; Beltran, AM; Fernandez, MA; Cadus, LE
Journal of Solid State Chemistry, 273 (2019) 75-80


LaAl1-xNixO3 (with x = 0.05 and 0.2) perovskite oxides were successfully synthesized and its behavior under reduction atmosphere was studied. HRTEM and STEM studies, coupled to HAADF and EDX detection, allowed to evidence the Ni exsolution process to the surface of the solid and to build nano-catalytic centers. The size of these centers is independent of the reduction conditions in the range studied. The high specific surface of the raw material, its porosity and the structure defects could be responsible of the low temperature at which the exsolution process starts. The content of Ni dopants allows the control of Ni centers size on the surface and the synthesis method provides Ni-nanoparticles strongly anchored to the resultant support.

May, 2019 | DOI: 10.1016/j.jssc.2019.02.036

Amber imitation? Two unusual cases of Pinus resin-coated beads in Iberian Late Prehistory (3rd and 2nd millennia BC)

Odriozola, CP; Cordero, JAG; Daura, J; Sanz, M; Martinez-Blanes, JM; Aviles, MA
PLoS One, 14 (2019) e0215469


A group of beads from the artificial cave of La Molina (Lora de Estepa, Sevilla) and Cova del Gegant (Sitges, Barcelona) were made from a biogenic raw material and intentionally covered by a layer of resin. This is the first time this type of treatment has been documented on elements of adornment in the Late Prehistory of the Iberian Peninsula. The composition and nature of the coatings are analysed and the symbolic role of such alterations and imitations of prehistoric adornments is discussed.

May, 2019 | DOI: 10.1371/journal.pone.0215469