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Artículos SCI

2017


Titulo: Characterization of ashes from greenhouse crops plant biomass residues using X-ray fluorescence analysis and X-ray diffraction
Autores: Garzon, E; Morales, L; Martinez-Blanes, JM; Sanchez-Soto, PJ
Revista: X-ray spectrometry, 46 (2017) 569-578
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A characterization of ashes obtained by thermal treatments on greenhouse crops plant biomass residues is presented. The chemical analysis, by X-ray fluorescence (wavelength-dispersive X-ray fluorescence), and phase analysis, by X-ray diffraction, of the resultant ashes are reported. Thermal treatments of selected samples of these residues increase the relative amounts of inorganic Mg, Si, P, and S in the ashes, being these amounts as high as increasing temperature. As an opposite effect, Na, Cl, and K contents decrease as increasing temperature by a volatilization process of the chlorides, as confirmed by X-ray diffraction. The crystalline phase analysis of the ashes demonstrates the formation of inorganic constituents of the biomass, including alkaline chlorides and calcium salts (calcite, anhydrite, and apatite). Progressive thermal treatments induce the formation of new silicate phases (akermanite and grossularite) and silica (-quartz and cristobalite). Furthermore, the particle size of the starting biomass samples does not influence the evolution of the crystalline phases by thermal treatments. In contrast, a previous leaching using water and subsequent heating at 1,000 degrees C produces the formation of periclase (MgO), lime (CaO), and the silicate gehlenite, without the presence of anhydrite. This study is interesting for future investigations on the residues as a profitable biomass source for energy production and sustainable large-scale management. Some potential applications of the resultant ashes can be proposed.

Noviembre, 2017 | DOI: 10.1002/xrs.2801

Titulo: Materials chemistry approaches to the control of the optical features of perovskite solar cells
Autores: Calvo, Mauricio E.
Revista: Journal of Materials Chemistry A, 5 (2017) 20561-20578
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Perovskite solar cells have revolutionized the field of photovoltaics. Apart from their impressive photo-conversion efficiencies, the ease of their fabrication – principally when carried out by solution processing – has permitted addition of new functionalities to the photovoltaic cell. Some of these features are related to the optical properties. In this review, the different materials chemistry approaches that allow controlling the spectral absorption of ABX3 perovskite layers and the changes that they produce in the visual aspect of the solar cell will be covered. These modifications can be done either by playing with the composition of the precursors or by integrating different types of nanostructures. Spectral bandgap tuning, semitransparency, color and enhancement of light absorption are examples of how these modifications operate in the core of ABX3 perovskite solar cells. These optical features bring benefits in terms of photo-conversion efficiencies or else in the aesthetical integration of perovskite solar cells with architectonic elements for building integrated photovoltaics. Additionally, surface passivation approaches are covered to show its effect over the photo-conversion efficiency and stability of the cell.

Octubre, 2017 | DOI: 10.1039/c7ta05666d

Titulo: Facile Synthesis of Hybrid Organic–Inorganic Perovskite Microcubes of Optical Quality Using Polar Antisolvents
Autores: Li, Yuelong; Galisteo-Lopez, Juan F.; Calvo, Mauricio E.; Miguez, Hernan
Revista: ACS Applied Materials & Interfaces, 9 (2017) 35505-35510
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Herein, we demonstrate a synthetic approach producing highly crystalline methylammonium lead bromide perovskite (MAPbBr3) microcubes at room temperature by injecting a perovskite precursor solution into an environmentally friendly antisolvent (isopropyl alcohol). Confirmed by X-ray and electron diffraction, as well as electron microscopy, these MAPbBr3 microcubes are single crystals and have perfect cubic structure, with sizes varying between 1 and 15 μm depending on the synthesis conditions. The stoichiometry of the MAPbBr3 crystal is proven by energy-dispersive X-ray analysis. Finally, optical analysis carried out by means of laser scanning confocal microscopy evidences how the crystalline quality of the microcubes translates into a homogeneous photoluminescence throughout the cube volume.

Octubre, 2017 | DOI: 10.1021/acsami.7b08431

Titulo: Towards Extending Solar Cell Lifetimes: Addition of a Fluorous Cation to Triple Cation-Based Perovskite Films
Autores: Salado, M; Fernandez, MA; Holgado, JP; Kazim, S; Nazeeruddin, MK; Dyson, PJ; Ahmad, S
Revista: Chemsuschem, 10 (2017) 3846-3853
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Organohalide perovskites have emerged as highly promising replacements for thin-film solar cells. However, their poor stability under ambient conditions remains problematic, hindering commercial exploitation. The addition of a fluorous-functionalized imidazolium cation during the preparation of a highly stable cesium-based mixed perovskite material Cs-0.05(MA(0.15)FA(0.85))(0.95)Pb(I0.85Br0.15)(3) (MA= methylammonium; FA= formamidinium) has been shown to influence its stability. The resulting materials, which vary according to the amount of the fluorous-functionalized imidazolium cation present during fabrication, display a prolonged tolerance to atmospheric humidity (> 100 days) along with power conversion efficiencies exceeding 16%. This work provides a general route that can be implemented in a variety of perovskites and highlights a promising way to increase perovskite solar cell stability.

Octubre, 2017 | DOI: 10.1002/cssc.201700797

Titulo: Defect chemistry and electrical properties of BiFeO3
Autores: Schrade, M; Maso, N; Perejon, A; Perez-Maqueda, LA; West, AR
Revista: Journal of Matrials Chemistry C, 5 (2017) 10077-10086
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BiFeO3 attracts considerable attention for its rich functional properties, including room temperature coexistence of magnetic order and ferroelectricity and more recently, the discovery of conduction pathways along ferroelectric domain walls. Here, insights into the defect chemistry and electrical properties of BiFeO3 are obtained by in situ measurements of electrical conductivity, sigma, and Seebeck coefficient, a, of undoped, cation-stoichiometric BiFeO3 and acceptor-doped Bi1-xCaxFeO3-delta ceramics as a function of temperature and oxygen partial pressure pO(2). Bi1-xCaxFeO3-delta exhibits p-type conduction; the dependencies of s and a on pO(2) show that Ca dopants are compensated mainly by oxygen vacancies. By contrast, undoped BiFeO3 shows a simultaneous increase of s and a with increasing pO(2), indicating intrinsic behavior with electrons and holes as the main defect species in almost equal concentrations. The pO(2)-dependency of s and a cannot be described by a single point defect model but instead, is quantitatively described by a combination of intrinsic and acceptor-doped characteristics attributable to parallel conduction pathways through undoped grains and defect-containing domain walls; both contribute to the total charge transport in BiFeO3. Based on this model, we discuss the charge transport mechanism and carrier mobilities of BiFeO3 and show that several previous experimental findings can readily be explained within the proposed model.

Octubre, 2017 | DOI: 10.1039/c7tc03345a

Titulo: Cellulose-polyhydroxylated fatty acid ester-based bioplastics with tuning properties: Acylation via a mixed anhydride system
Autores: Heredia-Guerrero, JA; Goldoni, L; Benitez, JJ; Davis, A; Ceseracciu, L; Cingolani, R; Bayer, IS; Heinze, T; Koschella, A; Heredia, A; Athanassiou, A
Revista: Carbohydrate Polymers, 173 (2017) 312-320
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The synthesis of microcrystalline cellulose (MCC) and 9,10,16-hydroxyhexadecanoic (aleuritic) acid ester-based bioplastics was investigated through acylation in a mixed anhydride (trifluoroacetic acid (TFA)/trifluoroacetic acid anhydride (TFAA)), chloroform co-solvent system. The effects of chemical interactions and the molar ratio of aleuritic acid to the anhydroglucose unit (AGU) of cellulose were investigated. The degree of substitution (DS) of new polymers were characterized by two-dimensional solution-state NMR and ranged from 0.51 to 2.60. The chemical analysis by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the presence of aleuritate groups in the structure induces the formation of new H-bond networks. The tensile analysis and the contact angle measurement confirmed the ductile behavior and the hydrophobicity of the prepared bioplastics. By increasing the aleuritate amounts, the glass transition temperature decreased and the solubility of bioplastic films in most common solvents was improved. Furthermore, this new polymer exhibits similar properties compared to commercial cellulose derivatives.

Octubre, 2017 | DOI: 10.1016/j.carbpol.2017.05.068

Titulo: HoF3 and DyF3 Nanoparticles as Contrast Agents for High-Field Magnetic Resonance Imaging
Autores: Gonzalez-Mancebo, Daniel; Becerro, Ana I.; Rojas, T. Cristina; Garcia-Martin, Maria L.; de la Fuente, Jesus M.; Ocana, Manuel
Revista: Particle & particle systems characterization, 34 (2017) art. 1700116
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Clinical contrast agents (CAs) currently used in magnetic resonance imaging (MRI) at low fields are less effective at high magnetic fields. The development of new CAs is mandatory to improve diagnostic capabilities of the new generation of high field MRI scanners. The purpose of this study is to synthesize uniform, water dispersible LnF3 (Ln = Ho, Dy) nanoparticles (NPs) and to evaluate their relaxivity at high magnetic field (9.4 T) as a function of size and composition. Two different types of HoF3 NPs are obtained by homogeneous precipitation in ethylene glycol at 120 °C. The use of holmium acetate as holmium precursor leads to rhombus-like nanoparticles, while smaller, ellipsoid-like nanoparticles are obtained when nitrate is used as the holmium salt. To explain this behavior, the mechanism of formation of both kinds of particles is analyzed in detail. Likewise, rhombus-like DyF3 nanoparticles are prepared following the same method as for the rhombus-like HoF3 nanoparticles. We have found, to the best of knowledge, the highest transverse relaxivity values at 9.4 T described in the literature for this kind of CAs. Finally, the LnF3 NPs have shown negligible cytotoxicity for C6 rat glioma cells for concentrations up to 0.1 mg mL−1.

Octubre, 2017 | DOI: 10.1002/ppsc.201700116

Titulo: Incorporation of Calcium Containing Mesoporous (MCM-41-Type) Particles in Electrospun PCL Fibers by Using Benign Solvents
Autores: Liverani, L.;Boccardi, E.; Beltrán, A.M.; Boccaccini, A.R.
Revista: Polymers, 9 (2017) 487
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The electrospinning technique is a versatile method for the production of fibrous scaffolds able to resemble the morphology of the native extra cellular matrix. In the present paper, electrospinning is used to fabricate novel SiO2particles (type MCM-41) containing poly(epsilon-caprolactone) (PCL) fibers. The main aims of the present work are both the optimization of the particle synthesis and the fabrication of composite fibers, obtained using benign solvents, suitable as drug delivery systems and scaffolds for soft tissue engineering applications. The optimized synthesis and characterization of calcium-containing MCM-41 particles are reported. Homogeneous bead-free composite electrospun mats were obtained by using acetic acid and formic acid as solvents; neat PCL electrospun mats were used as control. Initially, an optimization of the electrospinning environmental parameters, like relative humidity, was performed. The obtained composite nanofibers were characterized from the morphological, chemical and mechanical points of view, the acellular bioactivity of the composite nanofibers was also investigated. Positive results were obtained in terms of mesoporous particle incorporation in the fibers and no significant differences in terms of average fiber diameter were detected between the neat and composite electrospun fibers. Even if the Ca-containing MCM-41 particles are bioactive, this property is not preserved in the composite fibers. In fact, during the bioactivity assessment, the particles were released confirming the potential application of the composite fibers as a drug delivery system. Preliminary in vitro tests with bone marrow stromal cells were performed to investigate cell adhesion on the fabricated composite mats, the positive obtained results confirmed the suitability of the composite fibers as scaffolds for soft tissue engineering.

Octubre, 2017 | DOI: 10.3390/polym9100487

Titulo: Dense graphene nanoplatelet/yttria tetragonal zirconia composites: Processing, hardness and electrical conductivity
Autores: Gallardo-Lopez, A; Marquez-Abril, I; Morales-Rodriguez, A; Munoz, A; Poyato, R
Revista: Ceramics International, 43 (2017) 11743-11752
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Yttria tetragonal zirconia ceramic composites with 1, 2.5, 5 and 10 vol% nominal contents of graphene nanoplatelets (GNPs) were fabricated and characterized. First, the GNP dispersion in isopropanol was optimized to de-agglomerate the GNPs without damaging their structure. Then, submicrometric fully dense composites were obtained via spark plasma sintering (SPS) at 1250 degrees C with a 5 min holding time. The processing routine produced a nearly homogeneous GNP dispersion in the ceramic matrix, and the GNPs preferential orientation was perpendicular to the sintering compression axis. A ceramic grain refinement due to the GNPs was also detected. The Vickers hardness measured on the plane perpendicular to the sintering compression axis (basal plane) was lower than on the cross sections. This anisotropy increased with the increasing GNP content, while the average hardness decreased. The electrical conductivity was also highly anisotropic, up to seven times higher for the basal planes. The electrical percolation threshold for these composites was estimated to be between 2.2 and 4.4 vol% of the GNP measured content.

Octubre, 2017 | DOI: 10.1016/j.ceramint.2017.06.007

Titulo: Synthesis and characterization of Rh/MnO2-CeO2/Al2O3 catalysts for CO-PrOx reaction
Autores: Martinez, TLM; Laguna, OH; Lopez-Cartes, C; Centeno, MA
Revista: Molecular Catalysis, 440 (2017) 9-18
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Rh/MnO2-CeO2/Al2O3 catalysts with different manganese-to-ceria ratios have been synthesized, characterized and tested in CO-PrOx reaction. The physicochemical properties of the solids were studied by XRD, Raman spectroscopy, BET surface area, H-2-TPR, TGA-DTG and TEM. The differences observed in the textural, structural and redox properties were related to the Mn-to-ceria ratio of the samples. The segregation of Mn species was observed at high Mn-to-Ce ratios. In opposite way, MnO2-CeO2 solid solutions were obtained at low Mn to Ce ones. In this last case, the physicochemical properties of the solids were favored by the intimate Rh-Ce-Mn contact. The effect of the Mn-Ce presence on Rh catalysts which promotes the catalytic behavior towards selective CO oxidation was observed to be better at low temperatures. At higher temperatures, Mn species promote the Reverse Water Gas Shift reaction, whilst ceria promotes the H-2 oxidation in the whole range of working temperatures.

Octubre, 2017 | DOI: 10.1016/j.mcat.2017.06.018

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