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Facile Synthesis of Hybrid Organic–Inorganic Perovskite Microcubes of Optical Quality Using Polar Antisolvents

Li, Yuelong; Galisteo-Lopez, Juan F.; Calvo, Mauricio E.; Miguez, Hernan
ACS Applied Materials & Interfaces, 9 (2017) 35505-35510


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

Towards Extending Solar Cell Lifetimes: Addition of a Fluorous Cation to Triple Cation-Based Perovskite Films

Salado, M; Fernandez, MA; Holgado, JP; Kazim, S; Nazeeruddin, MK; Dyson, PJ; Ahmad, S
Chemsuschem, 10 (2017) 3846-3853


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

Defect chemistry and electrical properties of BiFeO3

Schrade, M; Maso, N; Perejon, A; Perez-Maqueda, LA; West, AR
Journal of Materials Chemistry C, 5 (2017) 10077-10086


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

Cellulose-polyhydroxylated fatty acid ester-based bioplastics with tuning properties: Acylation via a mixed anhydride system

Heredia-Guerrero, JA; Goldoni, L; Benitez, JJ; Davis, A; Ceseracciu, L; Cingolani, R; Bayer, IS; Heinze, T; Koschella, A; Heredia, A; Athanassiou, A
Carbohydrate Polymers, 173 (2017) 312-320


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

HoF3 and DyF3 Nanoparticles as Contrast Agents for High-Field Magnetic Resonance Imaging

Gonzalez-Mancebo, Daniel; Becerro, Ana I.; Rojas, T. Cristina; Garcia-Martin, Maria L.; de la Fuente, Jesus M.; Ocana, Manuel
Particle & particle systems characterization, 34 (2017) art. 1700116


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

Incorporation of Calcium Containing Mesoporous (MCM-41-Type) Particles in Electrospun PCL Fibers by Using Benign Solvents

Liverani, L.;Boccardi, E.; Beltrán, A.M.; Boccaccini, A.R.
Polymers, 9 (2017) 487


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

Dense graphene nanoplatelet/yttria tetragonal zirconia composites: Processing, hardness and electrical conductivity

Gallardo-Lopez, A; Marquez-Abril, I; Morales-Rodriguez, A; Munoz, A; Poyato, R
Ceramics International, 43 (2017) 11743-11752


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

Vapor and liquid optical monitoring with sculptured Bragg microcavities

Oliva-Ramirez, M; Gil-Rostra, J; Lopez-Santos, MC; Gonzalez-Elipe, AR; Yubero, F
Journal of Nanophotonics, 11 (2017) 046009


Sculptured porous Bragg microcavities (BMs) formed by the successive stacking of columnar SiO2 and TiO2 thin films with a zig-zag columnar microstructure are prepared by glancing angle deposition. These BMs act as wavelength-dependent optical retarders. This optical behavior is attributed to a self-structuration of the stacked layers involving the lateral association of nanocolumns in the direction perpendicular to the main flux of particles during the multilayer film growth, as observed by focused ion beam scanning electron microscopy. The retardance of these optically active BMs can be modulated by dynamic infiltration of their open porosity with vapors, liquids, or solutions with different refractive indices. The tunable birefringence of these nanostructured photonic systems has been successfully simulated with a simple model that assumes that each layer within the BMs stack has uniaxial birefringence. The sculptured BMs have been incorporated as microfluidic chips for optical transduction for label-free vapor and liquid sensing. Several examples of the detection performance of these chips, working either in reflection or transmission configuration, for the optical monitoring of vapor and liquids of different refractive indices and aqueous solutions of glucose flowing through the microfluidic chips are described.

Octubre, 2017 | DOI: 10.1117/1.JNP.11.046009

Synthesis and characterization of Rh/MnO2-CeO2/Al2O3 catalysts for CO-PrOx reaction

Martinez, TLM; Laguna, OH; Lopez-Cartes, C; Centeno, MA
Molecular Catalysis, 440 (2017) 9-18


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

High performance novel gadolinium doped ceria/yttria stabilized zirconia/nickel layered and hybrid thin film anodes for application in solid oxide fuel cells

Garcia-Garcia, FJ; Beltran, AM; Yubero, E; Gonzalez-Elipe, AR; Lambert, RM
Journal of Power Sources, 363 (2017) 251-259


Magnetron sputtering under oblique angle deposition was used to produce Ni-containing ultra thin film anodes comprising alternating layers of,gadolinium doped ceria (GDC) and yttria stabilized zirconia (YSZ) of either 200 nm or 1000 nm thickness. The evolution of film structure from initial deposition, through calcination and final reduction was examined by XRD, SEM, TEM and TOF-SIMS. After subsequent fuel cell usage, the porous columnar architecture of the two-component layered thin film anodes was maintained and their resistance to delamination from the underlying YSZ electrolyte was superior to that of corresponding single component Ni-YSZ and Ni-GDC thin films. Moreover, the fuel cell performance of the 200 nm layered anodes compared favorably with conventional commercially available thick anodes. The observed dependence of fuel cell performance on individual layer thicknesses prompted study of equivalent but more easily fabricated hybrid anodes consisting of simultaneously deposited Ni-GDC and Ni-YSZ, which procedure resulted in exceptionally intimate mixing and interaction of the components. The hybrids exhibited very unusual and favorable I-V characteristics, along with exceptionally high power densities at high currents. Their discovery is the principal contribution of the present work. 

Septiembre, 2017 | DOI: 10.1016/j.jpowsour.2017.07.085